Nitrile rubber polymer modifications

Although, the heat resistance of NBR is directly related to the increase in acrylonitrile content (ACN) of the elastomer, the presence of double bond in the polymer backbone makes it susceptible to heat, ozone, and light. Therefore, several strategies have been adopted to modify the nitrile rubber by physical and chemical methods in order to improve its properties and degradation behavior. The physical modification involves the mechanical blending of NBR with other polymers or chemical ingredients to achieve the desired set of properties. The chemical modifications, on the other hand, include chemical reactions, which impart structural changes in the polymer chain. 

The carboxylated types (XNBR) contain one, or more, acrylic type of acid as a terpolymer, the resultant chain being similar to nitrile except for the presence of carboxyl groups which occur about every 100 to 200 carbon atoms. This modification gives the polymer vastly improved abrasion resistance, higher hardness, higher tensile and tear strength, better low temperature brittleness, and better retention of physical properties after hot-oil and air ageing when compared to ordinary nitrile rubber. 

Chemical modification of polymers continues to be an active field of research [1-5]. It is a common means of changing and optimising the physical, mechanical and technological properties of polymers [5-7]. It is also a unique route to produce polymers with unusual chemical structure and composition that are otherwise inaccessible or very difficult to prepare by conventional polymerisation methods. For example, hydrogenated nitrile rubber (HNBR) which has a structure which resembles that of the copolymer ethylene and acrylonitrile, is very difficult to prepare by conventional copolymerisation of the monomers. Polyvinyl alcohol can only be prepared by hydrolysis of polyvinyl acetate. Most of the rubbers or rubbery materials have unsaturation in their main chain and/or in their pendent groups. So these materials are very susceptible towards chemical reactions compared to their saturated counterparts. 

Blends of butadiene-acrylonitrile copolymer rubber (nitrile rubber or NBR) and PVC are among the oldest known examples of commercial elastomer/ thermoplastic blends. The shortage of natural rubber during World War II stimulated research in the USA on the compounding and modification of synthetic polymers to produce rubber-like materials. An outcome of this research was the commercial introduction of NBR/PVC blends by B.F. Goodrich in 1947 under the trade name of Geon Polyblends [Pittenger and Cohan, 1947]. The blend showed improved ozone resistance and melt processability compared to the nitrile rubber (Table 15.12). 

Epoxy structural adhesives which employ carboxylic polybutadiene/acrylonitrile solid and liquid (CTBN) elastomers as modifiers have increased in number and proliferated in use since their introduction in the mid- 60 s. Such adhesive systems are now used in aircraft, electronics, automotive and industrial bonding operations. In the mid- 70 s, amine-reactive versions of the liquid polymers (ATBN) were issued, thereby offering another way to introduce rubber modification into a cured epoxy network. References are cited which provide detailed discussions of nitrile rubber, carboxylic nitrile rubber and both carboxyl- and amine-terminated nitrile liquid polymers (1-4). ... 

The comparison between the effects brought about during EB-irradiation of natural rubber, ethylene-propylene terpolymer (EPDM) and nitrile rubber emphasizes the satisfactory behavior of the last polymer [99C1, GOBI]. The gel fraction, chain scission and modification of the networks in these elastomers explain the changes in mechanical properties, i.e. the modulus increased and the elongation at break decreased with an increase in the irradiation dose (Fig. 66). 

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