Acrylate-styrene-acrylonitrile, mechanical

Acrylonitrile—Butadiene—Styrene. ABS is an important commercial polymer, with numerous apphcations. In the late 1950s, ABS was produced by emulsion grafting of styrene-acrylonitrile copolymers onto polybutadiene latex particles. This method continues to be the basis for a considerable volume of ABS manufacture. More recently, ABS has also been produced by continuous mass and mass-suspension processes (237). The various products may be mechanically blended for optimizing properties and cost. Brittle SAN, toughened by SAN-grafted ethylene—propylene and acrylate mbbets, is used in outdoor apphcations. Flame retardancy of ABS is improved by chlorinated PE and other flame-retarding additives (237). 

This study was therefore undertaken to prepare and evaluate acrylonitrile—butadiene-styrene (ABS) and methyl methacrylate-butadiene-styrene (MBS) polymers under similar conditions to determine whether replacement of acrylonitrile by methyl methacrylate could improve color stability during ultraviolet light aging, without detracting seriously from the good mechanical and thermal-mechanical properties of conventional ABS plastics. For purposes of control, the study also included briefer evaluation of commercial ABS, MBS, and acrylonitrile-butyl acrylate-styrene plastics. 

Catalysts of the Ziegler type have been used widely in the anionic polymerization of 1-olefins, diolefins, and a few polar monomers which can proceed by an anionic mechanism. Polar monomers normally deactivate the system and cannot be copolymerized with olefins. However, it has been found that the living chains from an anionic polymerization can be converted to free radicals in the presence of peroxides to form block polymers with vinyl and acrylic monomers. Vinylpyridines, acrylic esters, acrylonitrile, and styrene are converted to block polymers in good yield. Binary and ternary mixtures of 4-vinylpyridine, acrylonitrile, and styrene, are particularly effective. Peroxides are effective at temperatures well below those normally required for free radical polymerizations. A tentative mechanism for the reaction is given. 

The cyclopropanation of )- and (Z)-/S-methylstyrene (393 and 394) led to essentially the same ratio of ( ) and (Z) cyclopropane derivatives 395 and 396, indicating that the reactions proceeded stereospecihcally (81MI4 83BCJ2687). As electron-deficient olefins such as acrylate and acrylonitrile reacted even in the absence of copper(II) bromide, while the reaction of styrenes required the copper salt as catalyst, it was concluded that the reaction mechanism may vary, depending on the nature of the olefin. 

Vollmert presented 31 examples of multipolymer compositions, some of which were IPNs, (see Table 8.1). In example 20, a crosslinked poly(n-butyl acrylate) makes up network I. Poly(n-butyl acrylate-co-acrylonitrile) crosslinked with 1,4-butane-diol diacrylate makes up network II on a separate latex. A linear poly(styrene-co-acrylonitrile) latex makes up polymer III for a third latex. The three latexes are blended to form an impact-resistant polystyrene. This particular product, however, is not an IPN, because the two crosslinked latexes were polymerized and crosslinked separately and then mechanically blended together. 

Pdymerizations conducted so far have produced polymer coatii wifii a wi range of chemical and mechanical properties vtdiidi could be used to modify the carbon fiber-polymer matrix interphase of comptmt Helmed from fibers trrated by electropolymerization. A flexible polymer interphase could be introduced using systems such as methyl acrylate or VTBN, while stiffness could be adueved by using the styrene or styrene-acrylonitrile systems. Methyl methacrylate and styrene monomers would be expected to yield linear uncrosslinked polymer coatings while monomers which are multifunctional such as A,A -methylenebisacryiamide or multifunctional aziridines would be expected to crosslink in the systems they were used in. 

A number of ethylenic monomers and cyclic monomers undergo chain polymerization in the solid state when exposed to high-energy radiation (e.g. y-radiation). Examples include acrylamide, acrylic acid, acrylonitrile, vinyl acetate, styrene, 1,3,5-trioxane, propriolactone and hexamethylcyclo-trisiloxane. These polymerizations may involve free-radical and/or ionic species, but in most cases the precise mechanisms operating are not known. 

Copolymers of acrylonitrile [107-13-1] are used in extmsion and molding appHcations. Commercially important comonomers for barrier appHcations include styrene and methyl acrylate. As the comonomer content is increased, the permeabiUties increase as shown in Figure 3. These copolymers are not moisture-sensitive. Table 7 contains descriptions of three high nitrile barrier polymers. Barex and Cycopac resins are mbber-modified to improve the mechanical properties. 

Polymers in Schemes 12 and 13 were the first examples of the preparation of pyridinium and iminopyridinium ylide polymers. One of the more recent contributions of Kondo and his colleagues [16] deals with the sensitization effect of l-ethoxycarbonyliminopyridinium ylide (IPYY) (Scheme 14) on the photopolymerization of vinyl monomers. Only acrylic monomers such as MMA and methyl acrylate (MA) were photoinitiated by IPYY, while vinylacetate (VA), acrylonitrile (AN), and styrene were unaffected by the initiator used. A free radical mechanism was confirmed by a kinetic study. The complex of IPYY and MMA was defined as an exciplex that served as a precursor of the initiating radical. This ylide is unique in being stabilized by the participation of a... 

Kochi (1956a, 1956b) and Dickerman et al. (1958, 1959) studied the kinetics of the Meerwein reaction of arenediazonium salts with acrylonitrile, styrene, and other alkenes, based on initial studies on the Sandmeyer reaction. The reactions were found to be first-order in diazonium ion and in cuprous ion. The relative rates of the addition to four alkenes (acrylonitrile, styrene, methyl acrylate, and methyl methacrylate) vary by a factor of only 1.55 (Dickerman et al., 1959). This result indicates that the aryl radical has a low selectivity. The kinetic data are consistent with the mechanism of Schemes 10-52 to 10-56, 10-58 and 10-59. This mechanism was strongly corroborated by Galli s work on the Sandmeyer reaction more than twenty years later (1981-89). 

Poly (methyl methacrylate) was also subjected to mechanical reaction in a vibrating mill in common solvent for several monomers (ethylene, acrylic acid and its esters, acrylonitrile and styrene) at temperatures from —196 to 20° C (22). The formation of macroradicals and their reactions were followed by EPR (electron paramagnetic resonance). The macroradicals reacted with vinyl monomers at temperatures less than —100° C, while quinones underwent reaction as low as —196° C. The same experiments were performed also with polystyrene and polybutylenedimethacrylate. The radicals from polystyrene were more reactive than those from poly(methyl methacrylate). 

Several flexible polymers, such as natural rubber (NR) synthetic rubber (SR) polyalkyl acrylates copolymers of acrylonitrile, butadiene, and styrene, (ABS) and polyvinyl alkyl ethers, have been used to improve the impact resistance of PS and PVC. PS and copolymers of ethylene and propylene have been used to increase the ductility of polyphenylene oxide (PPO) and nylon 66, respectively. The mechanical properties of several other engineering plastics have been improved by blending them with thermoplastics. 

By chemical agents, indirect grafting on Nylon in liquid phase is frequently referred to in the bibliography. The most common reagent is air (144) or ozone, under controlled conditions, in order to avoid deterioration on the mechanical properties of the fiber, which is then immersed in the monomer. Hence, styrene (145-149), vinylidene chloride (146), vinyl acetate (146), acrylic and methacrylic acids (149), methyl methacrylate (146), acrylonitrile (146,148,149), 2-methyl-5-vinylpyridine (149) were successfully employed as grafting comonomers. 

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