ACRYLATE RUBBER

In 1984 the use of nitrile resins was re-approved by the Food and Drugs Administration with speeifie limits on the level of residual unreacted monomer. 

Another area of potential interest is in refrigerator liners. The move away from the ozone-layer-damaging chlorofluorocarbons (CFCs) to HCFCs in the USA and pentane/cyclopentane blends in Europe has not been without problems. These newer materials have an adverse effect on ABS whereas the nitrile resin appears satisfactory, if more expensive. 

Subsequently, several other companies have entered the acrylic rubber market (e.g. Thiokol, American Cyanamid, Goodyear, Polymer Corporation and US Rubber) and this has led to many technical developments. These may be categorised into the three main areas  

Whilst increasing the length of alkyl side chain can, to some extent, depress Tg and improve low-temperature properties this is at the expense of oil resistance. On the other hand lengthening of the side chain by incorporation of an —O— or an —S— linkage could often depress Tg and reduce swelling in hydrocarbon oils. This led to the commercial development of copolymers of either ethyl or butyl acrylate with an alkoxy acrylate comprising some 20-50% of the total composition. Typical of such alkoxy compounds are methoxyethyl acrylate (1) and ethoxyethyl acrylate (11)  

Because of processing problems 2-chloroethyl vinyl ether has now been replaced with other cure site monomers. These include vinyl and allyl chloracetates and allyl glycidyl ether. 

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Acrylic rubbers, as is the case for most specialty elastomers, are characterized by higher price and smaller consumption compared to general-purpose mbbers. The total mbber consumption ia 1991 was forecast (55) at 15.7 million t worldwide with a 66% share for synthetic elastomers (10.4 x 10 t). Acryhc elastomers consumption, as a minor amount of the total synthetic mbbers consumption, can hardly be estimated. As a first approximation, the ACM consumption is estimated to be 7000 t distributed among the United States, Western Europe, and Japan/Far East, where automotive production is significantly present. 

The rubbers may be vulcanised by conventional accelerated sulphur systems and also by peroxides. The vulcanisates are widely used in petrol hose and seal applications. Two limiting factors of the materials as rubbers are the tendency to harden in the presence of sulphur-bearing oils, particularly at elevated temperatures (presumably due to a form of vulcanisation), and the rather limited heat resistance. The latter may be improved somewhat by Judicious compounding to give vulcanisates that may be used up to 150°C. When for the above reasons nitrile rubbers are unsatisfactory it may be necessary to consider acrylic rubbers (Chapter 15), epichlorohydrin rubbers (Chapter 19) and in more extreme conditions fluororubbers (Chapter 13). 

In addition to poly(methyl methacrylate) plastics and polyacrylonitrile fibres, acrylic polymers find widespread use. First introduced in 1946, acrylic rubbers have become established as important special purpose rubbers with a useful combination of oil and heat resistance. Acrylic paints have become widely accepted particularly in the car industry whilst very interesting reactive adhesives, including the well-known super-glues are also made from acrylic polymers. 

The changes in acrylic rubber compounds have increased the scope of these materials as heat-and oil-resisting materials able to meet many of the increasingly stringent demands being imposed on rubbers for use in automotive applications. 

If polypropylene is too hard for the purpose envisaged, then the user should consider, progressively, polyethylene, ethylene-vinyl acetate and plasticised PVC. If more rubberiness is required, then a vulcanising rubber such as natural rubber or SBR or a thermoplastic polyolefin elastomer may be considered. If the material requires to be rubbery and oil and/or heat resistant, vulcanising rubbers such as the polychloroprenes, nitrile rubbers, acrylic rubbers or hydrin rubbers or a thermoplastic elastomer such as a thermoplastic polyester elastomer, thermoplastic polyurethane elastomer or thermoplastic polyamide elastomer may be considered. Where it is important that the elastomer remain rubbery at very low temperatures, then NR, SBR, BR or TPO rubbers may be considered where oil resistance is not a consideration. If, however, oil resistance is important, a polypropylene oxide or hydrin rubber may be preferred. Where a wide temperature service range is paramount, a silicone rubber may be indicated. The selection of rubbery materials has been dealt with by the author elsewhere. ... 

The particle size of the dispersed phase depends upon the viscosity of the elastomer-monomer solution. Preferably the molecular weight of the polybutadiene elastomer should be around 2 x 10 and should have reasonable branching to reduce cold flow. Furthermore, the microstructure of the elastomer provides an important contribution toward the low-temperature impact behavior of the final product. It should also be emphasized that the use of EPDM rubber [136] or acrylate rubber [137] may provide improved weatherability. It has been observed that with an increase in agitator speed the mean diameter of the dispersed phase (D) decreases, which subsequently levels out at high shear [138-141]. However, reagglomeration may occur in the case of bulk... 

Acrylated rubber Modified chlorinated rubber Bituminous Vinyl tar... 

Acrylated rubber These are based on styrene butadiene and have become commercially available only relatively recently. They are manufactured in several grades but most have the advantage over other materials in this class of being based on white spirit solvent rather than the stronger and more obnoxious xylol. In other respects, they are similar to chlorinated rubber and cost approximately the same, although they are easier to airless spray and the dried film contains less pores. They are considered to have superior weather resistance to chlorinated rubber and vinyl. 

FIGURE 3.3 (a) Transmission electron microscopic (TEM) image of acrylic rubber (ACM)-siUca hybrid nanocomposite synthesized from 10 wt% of tetraethoxysilane (TEOS). (From Bandyopadhyay, A., Bhowmick, A.K., and De Sarkar, M., J. Appl. Polym. Sci., 93, 2579, 2004. Courtesy of Wiley Interscience.) Transmission electron microscopic (TEM) photographs of acrylic rubber (ACM)-silica hybrid nanocomposites prepared from (b) 30 wt% and (c) 50 wt% tetraethoxysilane (TEOS) concentrations. (From Bandyopadhyay, A., Bhowmick, A.K., and De Sarkar, M., J. Appl. Polym. Sci., 93, 2579, 2004. Courtesy of Wiley InterScience.)... 

FIGURE 3.16 Morphology and visual appearance of acrylic rubber (ACM)-silica and epoxidized natural rubber (ENR)-silica hybrid composites prepared from different pH ranges (a) transmission electron microscopic (TEM) picture of ACM-siUca in pH 1.0-2.0, (b) scanning electron microscopic (SEM) picture of ACM-siUca in pH 5.0-6.0, (c) SEM image of ACM-siUca in pH 9.0-10.0, (d) TEM picture of ENR-silica in pH... 

FIGURE 3.17 Tensile stress-strain plots for uncross-linked acrylic rubber (ACM)-siUca and epoxidized natural rubber (ENR)-silica hybrid composites synthesized from various pH. Letter p in the legends indicates pH and the numbers following the letter are indicative of the pH ranges e.g., 1 means pH range of 1.0-2.0, similarly 3 means 3.0-4.0. (From Bandyopadhyay, A., De Sarkar, M., and Bhowmick, A.K., J. Mater. Sci., 41, 5981, 2006. Courtesy of Springer.)... 

TPEs prepared from rubber-plastic blends usually show poor high-temperature properties. This problem could be solved by using high-melting plastics like polyamides and polyesters. But, often they impart processing problems to the blends. Jha and Bhowmick [49] and Jha et al. [50] have reported the development and properties of novel heat and oil-resistant TPEs from reactive blends of nylon-6 and acrylate rubber (ACM). The properties of various thermoplastic compositions are shown in Table 5.4. In this kind of blend, the plastic phase forms the continuous phase, whereas... 

Typical Properties of Thermoplastic Elastomers Developed from Nylon-6-Acrylate Rubber Blends... 

Mechanical Properties of Thermoplastic Elastomers Based on Acrylate Rubber-Fluorocarbon Rubber-Polyacrylate Monomer... 

FIGURE 5.16 Viscosity-shear stress relationships for various compositions of nylon-6-acrylate rubber (ACM) blends at 240°C. 

Jha A. and Bhowmick A.K., Thermoplastic elastomeric blends of nylon 6/acrylate rubber Influence of interaction of mechanical and dynamic mechanical thermal properties. Rubber Chem. TechnoL, 70, 798, 1997. 

Jha A., Dutta B., and Bhowmick A.K., Effect of fillers and plasticizers on the performance of novel heat and oil-resistant thermoplastic elastomers from nylon-6 and acrylate rubber blends, J. Appl. Polym. Sci., 74, 1490, 1999. 

Kader M.A., Bhowmick A.K., Inoue T., and Chiba T. Morphology, mechanical and thermal behavior of acrylate rubber/fluorocarbon elastomer/poly aery late blends, J. Mat Sci., 37, 6789, 2002. 

Jha A., Bhowmick A.K., Eujitsuka R., and Inoue T. Interfacial interaction and peel adhesion between polyamide and acrylate rubber in thermoplastic elastomeric blends, J. Adhes. Sci. Technol., 13(6), 649, 1999. 

Wootthikanokkhan and Clythong have studied the effects of additive distribution and its effect on the distribution of cross-link density in NR-acrylic rubber (AR) blends [38]. The formulations of the four blends is given in Table 11.15. 

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