Butadiene acrylonitrile polymer

Durihg recent years a considerable amount of re-.search has been undertaken to understand what in the makeup of a polymer affects the processability. In the late 1980s, the Rubber Manufacturers Association in the United States undertook a research project with the Department of Polymer Engineering at the University of Akron to evaluate the laboratory equipment available using specially made butadiene-acrylonitrile polymers with different acrylonitrile levels, molecular weights, and molecular weight distributions. The results from the study confirmed that, from the processing variables viewpoint, the major factors are frequency (shear rate), temperature (temperature), and deformation (strain). 

An alternate approach was taken by a shaft seal manufacturer and a polymer producer working together [2]. The project involved making a series of butadiene-acrylonitrile polymers of known acrylonitrile contents with various molecular weights and molecular weight distributions then making seals under normal manufacturing conditions. There were four polymers evaluated ... 

Functionalized, liquid polybutadiene derivatives have also been developed as hybrid flexiblizers for epoxy resins. Carboxyl-terminated butadiene/acrylonitrile polymers, butadiene homopolymers, and maleic anhydride-amino acid grafted butadiene homopolymers have been used as flexibilizers to impart good low-temperature strength and water resistance to DGEBA-based epoxy adhesives. An epoxy system toughened by polybutadiene with maleic anhydride is claimed to provide a hydrophobic backbone, low viscosity, softness, and high tensile strength and adhesion (Table 7.10). 

The use of elastomeric or flexibilizing modifiers occurred and grew with epoxy resins first. Various aspects of toughened epoxy adhesives have been covered in reviews by the present authors (2,3), where the elastomeric modifiers have essentially been carboxylic, liquid and solid butadiene/acrylonitrile polymers. There has not been a systematic review, however, of these and other reactive liquid polybutadiene/acrylonitriles in the burgeoning areas of acrylic, anaerobic and radiation-curable systems. Thus, this paper s intent. 

R.S. Drake and W.J. McCarthy, "Liquid Butadiene/-Acrylonitrile Polymers with Reactive Terminals", Rubber World, Oct. 1968. 

The handbook of the International Institute of Synthetic Rubber Producers (IISRP) lists over 300 standard grades of butadiene-acrylonitrile polymers which are mainly differentiated by acrylonitrile content. The acrylonitrile content particularly influences the potential fluid resistance and low-temperature flexibility. 

Acrylonitrile—Butadiene—Styrene. Available only as sheet, ABS has good toughness and high impact resistance. It is readily therm oform able over a wide range of temperatures and can be deeply drawn. ABS has poor solvent resistance and low continuous-use temperature. It is often used in housings for office equipment (see Acrylonitrile polymers). 

The principal use of the peroxodisulfate salts is as initiators (qv) for olefin polymerisation in aqueous systems, particularly for the manufacture of polyacrylonitrile and its copolymers (see Acrylonitrile polymers). These salts are used in the emulsion polymerisation of vinyl chloride, styrene—butadiene, vinyl acetate, neoprene, and acryhc esters (see Acrylic ester polymers Styrene Vinyl polymers). 

Automotive appHcations account for about 116,000 t of woddwide consumption aimuaHy, with appHcations for various components including headlamp assembHes, interior instmment panels, bumpers, etc. Many automotive appHcations use blends of polycarbonate with acrylonitrile—butadiene—styrene (ABS) or with poly(butylene terephthalate) (PBT) (see Acrylonitrile polymers). Both large and smaH appHances also account for large markets for polycarbonate. Consumption is about 54,000 t aimuaHy. Polycarbonate is attractive to use in light appHances, including houseware items and power tools, because of its heat resistance and good electrical properties, combined with superior impact resistance. 

Synthetic. The main types of elastomeric polymers commercially available in latex form from emulsion polymerization are butadiene—styrene, butadiene—acrylonitrile, and chloroprene (neoprene). There are also a number of specialty latices that contain polymers that are basically variations of the above polymers, eg, those to which a third monomer has been added to provide a polymer that performs a specific function. The most important of these are products that contain either a basic, eg, vinylpyridine, or an acidic monomer, eg, methacrylic acid. These latices are specifically designed for tire cord solutioning, papercoating, and carpet back-sizing. 

Rubber-Modified Copolymers. Acrylonitrile—butadiene—styrene polymers have become important commercial products since the mid-1950s. The development and properties of ABS polymers have been discussed in detail (76) (see Acrylonitrile polymers). ABS polymers, like HIPS, are two-phase systems in which the elastomer component is dispersed in the rigid SAN copolymer matrix. The electron photomicrographs in Figure 6 show the difference in morphology of mass vs emulsion ABS polymers. The differences in stmcture of the dispersed phases are primarily a result of differences in production processes, types of mbber used, and variation in mbber concentrations. 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

Third Monomers. In order to achieve certain property improvements, nitrile mbber producers add a third monomer to the emulsion polymerization process. When methacrylic acid is added to the polymer stmcture, a carboxylated nitrile mbber with greatly enhanced abrasion properties is achieved (9). Carboxylated nitrile mbber carries the ASTM designation of XNBR. Cross-linking monomers, eg, divinylbenzene or ethylene glycol dimethacrylate, produce precross-linked mbbers with low nerve and die swell. To avoid extraction losses of antioxidant as a result of contact with fluids duriag service, grades of NBR are available that have utilized a special third monomer that contains an antioxidant moiety (10). FiaaHy, terpolymers prepared from 1,3-butadiene, acrylonitrile, and isoprene are also commercially available. 

As of 1992, the first specialty platable plastic, acrylonitrile—butadiene—styrene (ABS) terpolymer (see Acrylonitrile polymers, ABS resins), is used ia over 90% of POP appHcatioas. Other platable plastics iaclude poly(pheayleae ether) (see PoLYETPiERs), ayloa (see Polyamides), polysulfoae (see Polymers CONTAINING sulfur), polypropyleae, polycarboaate, pheaoHcs (see Pphenolic resins), polycarboaate—ABS alloys, polyesters (qv), foamed polystyreae (see Styrene plastics), and other foamed plastics (qv). 

Cellulose acetate butyrate, f Acrylonitrile butadiene styrene polymer. 

At one time butadiene-acrylonitrile copolymers (nitrile rubbers) were the most important impact modifiers. Today they have been largely replaced by acrylonitrile-butadiene-styrene (ABS) graft terpolymers, methacrylate-buta-diene-styrene (MBS) terpolymers, chlorinated polyethylene, EVA-PVC graft polymers and some poly acrylates. 

The common feature of these materials was that all contained a high proportion of acrylonitrile or methacrylonitrile. The Vistron product, Barex 210, for example was said to be produced by radical graft copolymerisation of 73-77 parts acrylonitrile and 23-27 parts by weight of methyl acrylate in the presence of a 8-10 parts of a butadiene-acrylonitrile rubber (Nitrile rubber). The Du Pont product NR-16 was prepared by graft polymerisation of styrene and acrylonitrile in the presence of styrene-butadiene copolymer. The Monsanto polymer Lopac was a copolymer of 28-34 parts styrene and 66-72 parts of a second monomer variously reported as acrylonitrile and methacrylonitrile. This polymer contained no rubbery component. 

Other polymers used in the PSA industry include synthetic polyisoprenes and polybutadienes, styrene-butadiene rubbers, butadiene-acrylonitrile rubbers, polychloroprenes, and some polyisobutylenes. With the exception of pure polyisobutylenes, these polymer backbones retain some unsaturation, which makes them susceptible to oxidation and UV degradation. The rubbers require compounding with tackifiers and, if desired, plasticizers or oils to make them tacky. To improve performance and to make them more processible, diene-based polymers are typically compounded with additional stabilizers, chemical crosslinkers, and solvents for coating. Emulsion polymerized styrene butadiene rubbers (SBRs) are a common basis for PSA formulation [121]. The tackified SBR PSAs show improved cohesive strength as the Mooney viscosity and percent bound styrene in the rubber increases. The peel performance typically is best with 24—40% bound styrene in the rubber. To increase adhesion to polar surfaces, carboxylated SBRs have been used for PSA formulation. Blends of SBR and natural rubber are commonly used to improve long-term stability of the adhesives. 

Acrylonitrile-butadiene-styrene polymers are similar in stmeture, but the acrylonitrile hardens the polymer. Minute rubber particles act as stress-relief centers, making it good for large objects luggage or car body parts. It can be chrome plated, foamed, injection molded, blown, and alloyed wiih other pla.siic. . 

Mehrabzadeh M. and Delfan N., Thermoplastic elastomers of butadiene-acrylonitrile copolymer and polyamide. VI. Dynamic crosslinking by different systems, J. Appl. Polym. Sci., 77, 2057, 2000. 

Aryloxyphosphazene copolymers can also confer fireproof properties to flammable materials when blended. Dieck [591] have used the copolymers III, and IV containing small amounts of reactive unsaturated groups to prepare blends with compatible organic polymers crosslinkable by the same mechanism which crosslinks the polyphosphazene, e.g. ethylene-propylene and butadiene-acrylonitrile copolymers, poly(vinyl chloride), unsaturated urethane rubber. These blends were used to prepare foams exhibiting excellent fire retardance and producing low smoke levels or no smoke when heated in an open flame. Oxygen index values of 27-56 were obtained. 

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