Acrylonitrile in copolymers

The presence of acrylonitrile in copolymers can also be demonstrated by heating a sample of the dry material in a test tube and testing with indicator paper for the formation of HCN. Prepare the indicator paper hy dissolving 0.3 g copper(ll) acetate in 100 ml water. Impregnate strips of filter paper, and then air-dry them. Just before use, dip the strips in a solution of 0.05 g benzidine in 100 ml 1IV acetic acid (prepared from equal parts of 2IV acetic acid and water). If HCN is formed and passes over the moist paper, the paper turns blue (Careful ). 

Styrene-Acrylonitrile (SAN) Copolymers. SAN resins are random, amorphous copolymers whose properties vary with molecular weight and copolymer composition. An increase in molecular weight or in acrylonitrile content generally enhances the physical properties of the copolymer but at some loss in ease of processing and with a slight increase in polymer color. 

Styrene—acrylonitrile (SAN) copolymers [9003-54-7] have superior properties to polystyrene in the areas of toughness, rigidity, and chemical and thermal resistance (2), and, consequendy, many commercial appHcations for them have developed. These optically clear materials containing between 15 and 35% AN can be readily processed by extmsion and injection mol ding, but they lack real impact resistance. 

The properties of SAN resins depend on their acrylonittile content. Both melt viscosity and hardness increase with increasing acrylonittile level. Unnotched impact and flexural strengths depict dramatic maxima at ca 87.5 mol % (78 wt %) acrylonitrile (8). With increasing acrylonitrile content, copolymers show continuous improvements in barrier properties and chemical and uv resistance, but thermal stabiUty deteriorates (9). The glass-transition... 

Acrylonitrile has been grafted onto many polymeric systems. In particular, acrylonitrile grafting has been used to impart hydrophilic behavior to starch (143—145) and polymer fibers (146). Exceptional water absorption capabiUty results from the grafting of acrylonitrile to starch, and the use of 2-acrylamido-2-methylpropanesulfonic acid [15214-89-8] along with acrylonitrile for grafting results in copolymers that can absorb over 5000 times their weight of deionized water (147). 

Monomer compositional drifts may also occur due to preferential solution of the styrene in the mbber phase or solution of the acrylonitrile in the aqueous phase (72). In emulsion systems, mbber particle size may also influence graft stmcture so that the number of graft chains per unit of mbber particle surface area tends to remain constant (73). Factors affecting the distribution (eg, core-sheU vs "wart-like" morphologies) of the grafted copolymer on the mbber particle surface have been studied in emulsion systems (74). Effects due to preferential solvation of the initiator by the polybutadiene have been described (75,76). 

Etherification and esterification of hydroxyl groups produce derivatives, some of which are produced commercially. Derivatives may also be obtained by graft polymerization wherein free radicals, initiated on the starch backbone by ceric ion or irradiation, react with monomers such as vinyl or acrylyl derivatives. A number of such copolymers have been prepared and evaluated in extmsion processing (49). A starch—acrylonitrile graft copolymer has been patented (50) which rapidly absorbs many hundred times its weight in water and has potential appHcations in disposable diapers and medical suppHes. 

The dynamic mechanical properties of VDC—VC copolymers have been studied in detail. The incorporation of VC units in the polymer results in a drop in dynamic modulus because of the reduction in crystallinity. However, the glass-transition temperature is raised therefore, the softening effect observed at room temperature is accompanied by increased brittleness at lower temperatures. These copolymers are normally plasticized in order to avoid this. Small amounts of plasticizer (2—10 wt %) depress T significantly without loss of strength at room temperature. At higher levels of VC, the T of the copolymer is above room temperature and the modulus rises again. A minimum in modulus or maximum in softness is usually observed in copolymers in which T is above room temperature. A thermomechanical analysis of VDC—AN (acrylonitrile) and VDC—MMA (methyl methacrylate) copolymer systems shows a minimum in softening point at 79.4 and 68.1 mol % VDC, respectively (86). 

Most of the surface sizes used in North America are modified styrene maleic anhydride (SMA) copolymers. Commercially available materials include Scripset (Monsanto/Hercules Inc.), Cypres (Cytec), Sursize (Akzo Nobel), MSA (Morton), NovaCote (Georgia Pacific), and HTl (Hopton Technologies). Styrene acrylate emulsions that are commonly used include Jetsize and Unibond (Akzo Nobel), Basoplast (BASF), and Cypres (Cytec). Other materials used as surface sizes include acrylonitrile acrylate copolymer (Basoplast, BASF), stearylated melamine resin (Sequapel, Sequa), polyurethane (Graphsize, Vining Chemicals), and diisobutylene maleic anhydride copolymers (Baysynthol, Bayer). 

During the 1970s there was considerable interest for a time in copolymers with a high acrylonitrile content for use as barrier resins, i.e. packaging materials with low permeability to gases. Problems associated with free acrylonitrile have, however, led to the virtual disappearance of these materials from the market. 

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. 

The term ABS was originally used as a general term to describe various blends and copolymers containing acrylonitrile, butadiene and styrene. Prominent among the earliest materials were physical blends of acrylonitrile-styrene copolymers (SAN) (which are glassy) and acrylonitrile-butadiene copolymers (which are rubbery). Such materials are now obsolete but are referred to briefly below, as Type 1 materials, since they do illustrate some basic principles. Today the term ABS usually refers to a product consisting of discrete cross-linked polybutadiene rubber particles that are grafted with SAN and embedded in a SAN matrix. 

The first approach has been important commercially. The monomer most commonly used is a-methylstyrene (see Section 16.11), whose polymer has a Tg of about 120°C. The heat distortion temperature of the resultant-ABS type polymer will depend on the level of replacement of styrene by the a-methyl-styrene. (It may be noted in passing that a-methylstyrene-acrylonitrile binary copolymers have been available as alternatives to styrene-acrylonitrile materials but have not achieved commercial significance.)... 

Rhodium- and cobalt-catalyzed hydrogenation of butadiene and 1-hexene [47, 48] and the Ru-catalyzed hydrogenation of aromatic compounds [49] and acrylonitrile-butadiene copolymers [50] have also been reported to be successful in ionic liquids. 

In our laboratory this kind of research has been systematically carried out for a number of years. A certain progress has been made in developing new promising methods for the chemical modification of PAN and acrylonitrile (AN) copolymers, and in creating new types of fibres with technologically valuable properties. 

The composition of block copolymers and, in particular, alternation of PAN and PEO blocks in the macromolecule of copolymers depends on the ratio between PEO and acrylonitrile in the reaction system. At low PEO concentrations in the reaction mixture a tri-block copolymer is probably formed with the following alternation of blocks ... 

Adhesion of end-sealing compounds Alcohol permeability of acrylonitrile-styrene copolymers. .. Alcoholic beverages stored in... 

The heterogeneous copolymerization of styrene and acrylonitrile in various diluents as reported by Riess and Desvalois (22). Although the copolymer composition in these studies was not strongly influenced by the diluent choice, the preferential adsorption of acrylonitrile monomer onto the polymer particles shifted the azeotropic copolymerization point from the 38 mole % acrylonitrile observed in solution to 55 mole % acrylonitrile. 

The principal use of acrylonitrile since the early 1950s has been in the manufacture of so-called acrylic textile fibers. Acrylonitrile is first polymerized to polyacrylonitrile, which is then spun into fiber. The main feature of acrylic fibers is their wool-like characteristic, making them desirable for socks, sweaters, and other types of apparel. However, as with all synthetic textile fibers, fashion dictates the market and acrylic fibers currently seem to be in disfavor, so this outlet for acrylonitrile may be stagnant or declining. The other big uses for acrylonitrile are in copolymers, mainly with styrene. Such copolymers are very useful for the molding of plastic articles with very high impact resistance. 

Coleman and Sivy also used an infrared transmission cell to undertake degradation studies under reduced pressure on a series of poly(acrylonitrile) (ACN) copolymers [30-33]. Thin films prepared from a polymer were mounted in the specially designed temperature-controlled cell mounted within the infrared spectrometer. The comparative studies were made on ACN copolymers containing vinyl acetate [30,32], methacrylic acid [30,31] and acrylamide [30,33]. The species monitored was the production of the cyclised pyridone structure. This was characterised in part by loss of C=N stretch (vC = N) intensity at 2,240 cm-1 accompanied by the appearance and increase in intensity of a doublet at 1,610/1,580 cm-1. 

Standard black O-rings made of an acrylonitrile-butadiene copolymer (such as Perbunan) have proved to be stable in HF at concentrations up to 50%. If contamination of the silicon sample is an issue, the nitrile O-rings may be replaced by vi-nylidene fluoride-hexafluoropropylene (Viton) O-rings [9],... 

Nitrile rubber has declined in importance, but has been replaced by styrene-acrylonitrile (SAN) copolymers and acrylonitrile-butadiene-styrene... 

Uses Copolymerized with methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, or 1,1-dichloroethylene to produce acrylic and modacrylic fibers and high-strength fibers ABS (acrylonitrile-butadiene-styrene) and acrylonitrile-styrene copolymers nitrile rubber cyano-ethylation of cotton synthetic soil block (acrylonitrile polymerized in wood pulp) manufacture of adhesives organic synthesis grain fumigant pesticide monomer for a semi-conductive polymer that can be used similar to inorganic oxide catalysts in dehydrogenation of tert-butyl alcohol to isobutylene and water pharmaceuticals antioxidants dyes and surfactants. 

Compositionally uniform copolymers of tributyltin methacrylate (TBTM) and methyl methacrylate (MMA) are produced in a free running batch process by virtue of the monomer reactivity ratios for this combination of monomers (r (TBTM) = 0.96, r (MMA) = 1.0 at 80°C). Compositional ly homogeneous terpolymers were synthesised by keeping constant the instantaneous ratio of the three monomers in the reactor through the addition of the more reactive monomer (or monomers) at an appropriate rate. This procedure has been used by Guyot et al 6 in the preparation of butadiene-acrylonitrile emulsion copolymers and by Johnson et al (7) in the solution copolymerisation of styrene with methyl acrylate. 

Figure 3.5 shows aTEM picture of the core/double shell latex particles incorporated into an styrene/acrylonitrile (SAN) copolymer matrix (thin cut through the particle-filled matrix).The particles are very homogeneous in size and can also be used to prepare ar-tifical opals. 

An appropriate formalism for Mark-Houwink-Sakurada (M-H-S) equations for copolymers and higher multispecies polymers has been developed, with specific equations for copolymers and terpolymers created by addition across single double bonds in the respective monomers. These relate intrinsic viscosity to both polymer MW and composition. Experimentally determined intrinsic viscosities were obtained for poly(styrene-acrylonitrile) in three solvents, DMF, THF, and MEK, and for poly(styrene-maleic anhydride-methyl methacrylate) in MEK as a function of MW and composition, where SEC/LALLS was used for MW characterization. Results demonstrate both the validity of the generalized equations for these systems and the limitations of the specific (numerical) expressions in particular solvents. 

Average copolymer compositions of SAN samples were determined by elemental analysis, yielding weight percent acrylonitrile in the polymer. Compositions of S/MA and S/MA/MM were determined by sequential hydrolysis and pyridine titration to obtain maleic anhydride content and by infrared analysis for methyl methacrylate content. 

Butadiene—Acrylonitrile Latices. Nitrile latices are copolymers of butadiene and acrylonitrile in which those copolymerized monomers are the main constituents (see Elastomers, SYNTHETIC-NITRILE rubber). The latices differ mainly in ratio of comonomer and stabilizer type. They can be classified as low and medium acrylonitrile (ACN) types. The latter contain 35—40 wt % nitrile mbber, and low types ca 27—29 wt %. 

The chemical intermediates adiponitrile and acrylamide have surpassed nitrile rubbers as end-use products of acrylonitrile in the United States and Japan. Adiponitrile is further converted to hexamethylenediamine (HMDA), which is used to manufacture nylon 6/6. Acrylamide is used to produce water-soluble polymers or copolymers used for paper manufacturing, waste treatment, mining applications and enhanced oil recovery (Langvardt, 1985 Brazdil, 1991). 

---