Natural rubber mechanism

There is much evidence that weak links are present in the chains of most polymer species. These weak points may be at a terminal position and arise from the specific mechanism of chain termination or may be non-terminal and arise from a momentary aberration in the modus operandi of the polymerisation reaction. Because of these weak points it is found that polyethylene, polytetrafluoroethylene and poly(vinyl chloride), to take just three well-known examples, have a much lower resistance to thermal degradation than low molecular weight analogues. For similar reasons polyacrylonitrile and natural rubber may degrade whilst being dissolved in suitable solvents. 

Natural rubber displays the phenomenon known as natural tack. When two clean surfaces of masticated rubber (rubber whose molecular weight has been reduced by mechanical shearing) are brought into contact the two surfaces become strongly attached to each other. This is a consequence of interpenetration of molecular ends followed by crystallisation. Amorphous rubbers such as SBR do not exhibit such tack and it is necessary to add tackifiers such as rosin derivatives and polyterpenes. Several other miscellaneous materials such as factice, pine tar, coumarone-indene resins (see Chapter 17) and bitumens (see Chapter 30) are also used as processing aids. 

By rolling on a two-roll mill the molecular weight of the polymer can be greatly reduced by mechanical scission, analogous to that involved in the mastication of natural rubber, and so mouldable materials may be obtained. However, bulk polymerisation is expensive and the additional milling and grinding processes necessary make this process uneconomic in addition to increasing the risk of contamination. 

The important properties of the rubbers are their temperature stability, retention of elasticity at low temperatures and good electrical properties. They are much more expensive than the conventional rubbers (e.g. natural rubber and SBR) and have inferior mechanical properties at room temperature. 

Mention may finally be made of graft polymers derived from natural rubber which have been the subject of intensive investigation but which have not achieved commercial significance. It has been found that natural rubber is an efficient chain transfer agent for free-radical polymerisation and that grafting appears to occur by the mechanism shown in Figure 30.8. 

As with c -polyisoprene, the gutta molecule may be hydrogenated, hydro-chlorinated and vulcanised with sulphur. Ozone will cause rapid degradation. It is also seriously affected by both air (oxygen) and light and is therefore stored under water. Antioxidants such as those used in natural rubber retard oxidative deterioration. If the material is subjected to heat and mechanical working when dry, there is additional deterioration so that it is important to maintain a minimum moisture content of 1%. (It is not usual to vulcanise the polymer.)... 

Two processes to natural rubber PSA tapes are outlined in Fig. 3, starting from the mechanically broken down rubber. The first route compounds the rubber with... 

In the earlier art, there was some consideration that partial incompatibility of the tackifier resin with the rubber was responsible for the appearance of tack, but this no longer is seriously held in light of continuing studies by many investigators. Aubrey [38] has addressed this in his review of the mechanism of tackification and the viscoelastic nature of pressure sensitive adhesives. Chu [39] uses the extent of modulus depression with added tackifier as a measure of compatibility. Thus in a plot of modulus vs. tackifier concentration, the resin that produces the deepest minimum is the most compatible. On this basis, Chu rates the following resins in order of compatibility for natural rubber rosin ester > C-5 resin > a-pinene resin > p-pinene resin > aromatic resin. 

Tackifying resins enhance the adhesion of non-polar elastomers by improving wettability, increasing polarity and altering the viscoelastic properties. Dahlquist [31 ] established the first evidence of the modification of the viscoelastic properties of an elastomer by adding resins, and demonstrated that the performance of pressure-sensitive adhesives was related to the creep compliance. Later, Aubrey and Sherriff [32] demonstrated that a relationship between peel strength and viscoelasticity in natural rubber-low molecular resins blends existed. Class and Chu [33] used the dynamic mechanical measurements to demonstrate that compatible resins with an elastomer produced a decrease in the elastic modulus at room temperature and an increase in the tan <5 peak (which indicated the glass transition temperature of the resin-elastomer blend). Resins which are incompatible with an elastomer caused an increase in the elastic modulus at room temperature and showed two distinct maxima in the tan <5 curve. 

Natural rubber was the only polymer for elastomer production until the advent of synthetics. Natural rubber, however, continues to maintain its competitive edge due mainly to the gain in properties such as high resilience, low hysteresis, low heat buildup, and excellent tack with mechanical properties achieved through the process of vulcanization [114-115]. The industry is said to be self-sufficient with a good technological base and is expected to compete successfully with synthetics because of the edge in properties mentioned above [116,117]. 

Compatibility and various other properties such as morphology, crystalline behavior, structure, mechanical properties of natural rubber-polyethylene blends were investigated by Qin et al. [39]. Polyethylene-b-polyiso-prene acts as a successful compatibilizer here. Mechanical properties of the blends were improved upon the addition of the block copolymer (Table 12). The copolymer locates at the interface, and, thus, reduces the interfacial tension that is reflected in the mechanical properties. As the amount of graft copolymer increases, tensile strength and elongation at break increase and reach a leveling off. 

The reactive extrusion of polypropylene-natural rubber blends in the presence of a peroxide (1,3-bis(/-butyl per-oxy benzene) and a coagent (trimethylol propane triacrylate) was reported by Yoon et al. [64]. The effect of the concentration of the peroxide and the coagent was evaiuated in terms of thermal, morphological, melt, and mechanical properties. The low shear viscosity of the blends increased with the increase in peroxide content initially, and beyond 0.02 phr the viscosity decreased with peroxide content (Fig. 9). The melt viscosity increased with coagent concentration at a fixed peroxide content. The morphology of the samples indicated a decrease in domain size of the dispersed NR phase with a lower content of the peroxide, while at a higher content the domain size increases. The reduction in domain size... 

Elastomers, of which vulcanized natural rubber is the most important example, also undergo dramatic changes in mechanical properties when filled with particulate solids. In part, knowledge of this particular type of system has been developed empirically as the technology of car-tyre manufacture has advanced. 

The results of mechanical properties (presented later in this section) showed that up to 20 phr, the biofillers showed superior strength and elongation behavior than CB, cellulose being the best. After 30 phr the mechanical properties of biocomposites deteriorated because of the poor compatibility of hydrophilic biopolymers with hydrophobic natural rubber(results not shown). While increasing quantity of CB in composites leads to constant increase in the mechanical properties. Scanning electron micrographs revealed presence of polymer-filler adhesion in case of biocomposites at 20 phr. 

A.H. Muhr, A.G. Thomas, and J.K. Varkey, A fracture mechanics study of natural rubber-to-metal bond failure, J. Adhesion Set TechnoL, 10, 593-616, 1996. 

This is the most widely used naturally occurring rubber. The literature search shows that many research groups have prepared nanocomposites based on this rubber [29-32]. Varghese and Karger-Kocsis have prepared natural rubber (NR)-based nanocomposites by melt-intercalation method, which is very useful for practical application. In their study, they have found increase in stiffness, elongation, mechanical strength, and storage modulus. Various minerals like MMT, bentonite, and hectorite have been used. 

Chemical pretreatments with amines, silanes, or addition of dispersants improve physical disaggregation of CNTs and help in better dispersion of the same in rubber matrices. Natural rubber (NR), ethylene-propylene-diene-methylene rubber, butyl rubber, EVA, etc. have been used as the rubber matrices so far. The resultant nanocomposites exhibit superiority in mechanical, thermal, flame retardancy, and processibility. George et al. [26] studied the effect of functionalized and unfunctionalized MWNT on various properties of high vinyl acetate (50 wt%) containing EVA-MWNT composites. Figure 4.5 displays the TEM image of functionalized nanombe-reinforced EVA nanocomposite. 

Chattopadhyay S., Chaki T.K., and Bhowmick A.K., New thermoplastic elastomers from poly(ethyle-neoctene) (engage), poly(ethylene-vinyl acetate) and low-density polyethylene by electron beam technology structural characterization and mechanical properties. Rubber Chem. TechnoL, 74, 815, 2001. Roy Choudhury N. and Dutta N.K., Thermoplastic elastomeric natural rubber-polypropylene blends with reference to interaction between the components. Advances in Polymer Blends and Alloys Technology, Vol. 5 (K. Finlayson, ed.), Technomic Publishers, Pensylvania, 1994, 161. 

Choudhury N.R., Chaki T.K., Dutta A., and Bhowmick A.K. Thermal, x-ray and d3mamic mechanical properties of thermoplastic elastomeric natural rubber-polyethylene blends. Polymer, 30, 2047, 1989. Marasch M.J., TPU s Growth from versatility, 53rd Annual Tech. Conference, Antech 95 4088, Boston, May 7-11, 1995. 

Roy Choudhury N. and Bhowmick A.K., Adhesion between individual components and mechanical properties of natural rubber-polypropylene thermoplastic elastomeric blends, J. Adhes. Sci. Technol., 2(3), 167, 1988. 

FIGURE 11.29 Effect of grafted natural rubber content on the mechanical properties of STR5L-PMMA blends at ratios of 50 50 ( ) and 70 30 ( ). (From Suriyachi, P., Kiatkamjomwong, S., and Prasassarkich, P., Rubber Chem. Technol., 77, 914, 2004.)... 

The molecular weight of natural rubber (NR) can be altered by mechanical means. Mastication of NR results in a reduction of molecular weight. In the distant past, NR was commonly subjected to mechanical degradation on open mills for extended periods of time to improve processability. 

Saintier, N., Multiaxial fatigue life of a natural rubber crack initiation mechanisms and local fatigue life criterion, Ph.D. dissertation, Ecole des Mines de Paris, 2001. 

Al-Malaika, S. and Amir, E.J., Thermoplastic elastomers Part III—Ageing and mechanical properties of natural rubber-reclaimed rubber/polypropylene systems and their role as solid phase dispersants in polypropylene/polyethylene blends, Polym. Degrad. Stab., 26, 31, 1989. 

Nitrile rubbers have high resistance to oils and organic solvents, and, although their mechanical properties are not as good as those of natural rubber, they are subject to much less deterioration in the presence of oils and solvents. They are not resistant to ozone attack. 

Another palladium complex, namely, a six-membered cyclopalladate complex of 2-benzoyl pyridine, has also been used for the hydrogenation of polymers [77, 78]. Possible catalytic mechanisms for the hydrogenation of natural rubber [76] and NBR [77] catalyzed by these two complexes were proposed, but unfortunately the authors did not provide sufficient evidence to support their proposed mechanisms. 

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