Acrylonitrile methyl methacrylate

Gerken and Ritchey [190] reported the C-NMR of series of acrylonitrile-methyl methacrylate (A/M) copolymers and determined the copolymer microstructure. They reported the configuration probabilities of A/M copolymers and Bernoullian statistics were found to describe the monomer configuration, a result in conflict with the conclusions of Pham [191]. Gerken and Ritchey [190] assigned the resonance lines of carbonyl and nitrile carbons to different triad cotactic sequences on the assumption that M and A monomer units have the same sensitivity to the tacticity of an adjacent A monomer unit. Also they did not calculate cotactic triad fractions from C-NMR spectra and did not compare experimental cotactic triad fractions with those expected from configurational probabilities have been made. 

Kapur and Brar [192] report the C-NMR spectra of a series of acrylonitrile-methyl methacrylate copolymers. The primary structure, including monomer composition, monomer sequence distribution and triad tacticity of A/M copolymers were determined on the basis of C[ H]-NMR analysis and compared with the calculated fractions. The resonance of carbonyl and nitrile carbons were assigned to different cotactic triads by considering the possible electronic interactions between the central monomer unit and its immediate neighbours. 

Reprinted with permission from AS. Brar and A. Sunita, Journal of Polymer  

6 Methacrylonitrile-vinylidene Cyanide (MAA-VCN) and Cyano-vinyl Acetate-vinylidene Cyanide (CVA-VCN) 

Reprinted from J.P. Montheard, A. Mesli, A. Belfkira, M. Raihane and Q-T. Pham, Macromolecular Reports, 1994, A31,1. 1994, Marcel Dekker [194]  

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Figure 7.6 Chemical shift (from hexamethyldisiloxane) for acrylonitrile-methyl methacrylate copolymers of the indicated methyl methacylate (Mj) content. Methoxyl resonances are labeled as to the triad source. [From R. Chujo, H. Ubara, and A. Nishioka, Polym. J. 3 670 (1972).]...

A third source of initiator for emulsion polymerisation is hydroxyl radicals created by y-radiation of water. A review of radiation-induced emulsion polymerisation detailed efforts to use y-radiation to produce styrene, acrylonitrile, methyl methacrylate, and other similar polymers (60). The economics of y-radiation processes are claimed to compare favorably with conventional techniques although worldwide iadustrial appHcation of y-radiation processes has yet to occur. Use of y-radiation has been made for laboratory study because radical generation can be turned on and off quickly and at various rates (61). 

Hydrogen cyanide is a reactant in the production of acrylonitrile, methyl methacrylates (from acetone), adiponitrile, and sodium cyanide. It is also used to make oxamide, a long-lived fertilizer that releases nitrogen steadily over the vegetation period. Oxamide is produced by the reaction of hydrogen cyanide with water and oxygen using a copper nitrate catalyst at about 70°C and atmospheric pressure ... 

Several radical copolymerizations of vinyl 2-furoate with well-known monomers (50 50) were also studied. Complete inhibition was obtained with vinyl acetate, very strong retardation with styrene, vinyl chloride and acrylonitrile methyl methacrylate homopolymerized without appreciable decrease in rate. It is evident that the degree of retardation that vinyl 2-furoate imposes upon the other monomer depends on the stability of the latter s free radical. With styrene and vinyl chloride the small amounts of fairly low molecular-weight products contained units from vinyl 2-furoate which had entered the chain both through the vinyl bond and through the ring (infrared band at 1640 cm-1). 

The activity of transition metal allyl compounds for the polymerization of vinyl monomers has been studied by Ballard, Janes, and Medinger (10) and their results are summarized in Table II. Monomers that polymerize readily with anionic initiators, such as sodium or lithium alkyls, polymerize vigorously with allyl compounds typical of these are acrylonitrile, methyl methacrylate, and the diene isoprene. Vinyl acetate, vinyl chloride, ethyl acrylate, and allylic monomers do not respond to these initiators under the conditions given in Table II. 

Fig. 56. Dependence of specific refractive index increment on conversion of monomers to polymer for a styrene/acrylonitrile/methyl methacrylate terpolymer in methyl ethyl ketone at 20 °C and 436 nm. (a) - partial azeotrope, (b) terpolymer with composition distribution163 ...

Deters (14) grafted acrylonitrile, methyl methacrylate and vinyl chloride on cellulose and cellulose triacetate. The first two monomers were put in the reactor as liquids, the last as a gas. The results are summarized on Table 1. Vinyl chloride did not graft to cellulose (14). 

Vinyl monomers studied were acrylonitrile, methyl methacrylate and methacrylic acid The toxicity or hazardous nature of ferric azide is not given in Sax nor were there found any other expl props repotted in the literature (Refs 7 8)... 

A critical appreciation of this review shows that there has been a large interest on the subject in the last twenty years. Most of the papers and patents deal with immersion techniques. Irradiation with gamma-rays seems to be the field to which more attention has been given. Practically all common unsaturated monomers have been studied more or less extensively, in specially styrene, acrylonitrile, methyl methacrylate, and vinyl acetate, respectively. In more recent years, grafts have been attached to the backbone polymer through reactions of the branch polymer with active centers generated on the polyamide matrix. 

Kargin, Usmanov, and Aikhodzhaev (64) used a similar technique of ozonization to introduce hydroperoxide groups into cellulose substrates. They observed grafting of styrene to ozonized viscose tire cord even without the presence of any other initiating system imparting improved rubber-adhesion to the rayon tire cord. In a later report, Usmanov, Aikhodzhaev, and Azizov (65) described the grafting of acrylonitrile, methyl methacrylate, methylvinylpyridine, and of vinylacetate onto ozonized cellulose. 

Also other oxidants have been used successfully to initiate graft copolymerization onto cellulose substrates. Toyo Rayon (79) achieved grafting by pretreatment of viscose rayon fibers with potassium permanganate-sulfuric acid and contacting it subsequently with acrylonitrile. Methyl methacrylate is being grafted to rayon when heated together with potassium bromate, as claimed by Asahi Chemical Industry... 

Polymer Components Firestone FR-S-2004 59.2% polybutadiene latex (polybutadiene equivalent) styrene acrylonitrile methyl methacrylate Dispersion Medium deionized distilled water (total)... 

ABA ABS ABS-PC ABS-PVC ACM ACS AES AMMA AN APET APP ASA BR BS CA CAB CAP CN CP CPE CPET CPP CPVC CR CTA DAM DAP DMT ECTFE EEA EMA EMAA EMAC EMPP EnBA EP EPM ESI EVA(C) EVOH FEP HDI HDPE HIPS HMDI IPI LDPE LLDPE MBS Acrylonitrile-butadiene-acrylate Acrylonitrile-butadiene-styrene copolymer Acrylonitrile-butadiene-styrene-polycarbonate alloy Acrylonitrile-butadiene-styrene-poly(vinyl chloride) alloy Acrylic acid ester rubber Acrylonitrile-chlorinated pe-styrene Acrylonitrile-ethylene-propylene-styrene Acrylonitrile-methyl methacrylate Acrylonitrile Amorphous polyethylene terephthalate Atactic polypropylene Acrylic-styrene-acrylonitrile Butadiene rubber Butadiene styrene rubber Cellulose acetate Cellulose acetate-butyrate Cellulose acetate-propionate Cellulose nitrate Cellulose propionate Chlorinated polyethylene Crystalline polyethylene terephthalate Cast polypropylene Chlorinated polyvinyl chloride Chloroprene rubber Cellulose triacetate Diallyl maleate Diallyl phthalate Terephthalic acid, dimethyl ester Ethylene-chlorotrifluoroethylene copolymer Ethylene-ethyl acrylate Ethylene-methyl acrylate Ethylene methacrylic acid Ethylene-methyl acrylate copolymer Elastomer modified polypropylene Ethylene normal butyl acrylate Epoxy resin, also ethylene-propylene Ethylene-propylene rubber Ethylene-styrene copolymers Polyethylene-vinyl acetate Polyethylene-vinyl alcohol copolymers Fluorinated ethylene-propylene copolymers Hexamethylene diisocyanate High-density polyethylene High-impact polystyrene Diisocyanato dicyclohexylmethane Isophorone diisocyanate Low-density polyethylene Linear low-density polyethylene Methacrylate-butadiene-styrene... 

Wooding and Higginson (94) have polymerized acrylonitrile, methyl methacrylate, styrene and butadiene with a wide variety of alkoxides and other basic materials. The ease of polymerization of monomer is in the above mentioned order. A further study of the polymerization of acrylonitrile by Zilka, Feit, and Frankel using alkoxides has also been reported (104). These workers also studied the polymerization of acrylonitrile and methacrylonitrile in dimethyl-formamide by aqueous quaternary ammonium hydroxides (106). 

Vinyl monomers that can be grafted to cellulose to achieve adhesive properties are acrylic acid, acrylonitrile, methyl methacrylate, and many others. Graft copolymers of cellulose derivatives have also found use as adhesives. For example, vinylacetate-grafted hydroxyethylcellulose can be used as an adhesive for packaging and tile ( ). Grafting of vinyl monomers onto lignocellulosic materials can convert them into suitable adhesive materials (0). 

The value of the exponent in eqn. (106) lies in the range 1 m 2. Monomers of widely differing polarity represent the extreme case with m = 2. This behaviour is observed, for example, with the pairs styrene—methyl methacrylate and acrylonitrile—methyl methacrylate. The other extreme, represented by the condition (105), was observed in copolymerizing monomers of very similar polarity with m = 1 (e. g. styrene—isoprene). The rate of co-addition generally increases with increasing temperature, and m decreases to 1, even for very dissimilar monomers (acrylonitrile—methyl methacrylate [194]). 

Now we move on to consider the analysis of copolymers. There are usually two things we would like to know. First, the composition of the copolymer and, second, some measure of sequence distributions. Again, in the early years, before the advent of commercial NMR instruments, infrared spectroscopy was the most widely used tool. The problem with the technique is that it requires that the spectrum contain bands that can be unambiguously assigned to specific functional groups, as in the (transmission) spectrum of an acrylonitrile/methyl methacrylate copolymer shown in Figure 7-43 (you can tell this is a really old spectrum, not only because it is plotted in transmission, but also because the frequency scale is in microns). 

FIGURE 7-43IR spectrum of an acrylonitrile/ methyl methacrylate copolymer [redrawn from an original figure in R. Zbinden, Infrared Spectroscopy of High Polymers, Academic Press, (1964)]. 

Popov. K.. Production of new polymer products with flocculating properties by the Mannich amino methylation of prehydiolized ternary acrylonitrile-methyl methacrylate-sodium vinylsulfonate copolymers. Tr. Vo-dosnahdyavane, Kamliz. Sanil. Tekh., 12, 119, 1977 Chem. Absir., 87, 18.5004, 1977. 

Roylance et al. studied yielding at temperatures between 0 and 75 °C in AMBS polymers, which are poly (styrene-acrylonitrile-methyl methacrylate) copolymers containing polybutadiene particles, and showed that Eq. (5) is obeyed over three decades of strain rate ). Nominal mbber contents varied between 0 and 13%, and the slopes of the Eyring curves changed with rubber content in the direction predicted by Eq. (8). As mbber phase volumes are not given, the data cannot be... 

The importance of cyanides in commerce is indicated by the annual U.S. production capacity for HCN which, in 2004, was estimated to be over 1 billion pounds. Approximately one-half of the U.S. production is used to prepare adiponitrile for nylon 66. Its other uses include the preparation of acrylonitrile, methyl methacrylate (via acetone cyanohydrin), methionine, and cyanide salts. 

Acrylonitrile Methyl methacrylate Styrene Vinyl Acetate Vinyl Chloride... 

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