Methyl acrylonitrile

Styrene Acrylonitrile Methyl acrylate Vinyl acetate... 

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).]...

Acrylonitrile—methyl acrylate—iadene terpolymers, by themselves, or ia blends with acrylonitrile—methyl acrylate copolymers, exhibit even lower oxygen and water permeation rates than the iadene-free copolymers (110,111). Terpolymers of acrylonitrile with iadene and isobutjlenealso exhibit excellent barrier properties (112), and permeation of gas and water vapor through acrylonitrile—styrene—isobutjleneterpolymers is also low (113,114). 

The monomer pair, acrylonitrile—methyl acrylate, is close to being an ideal monomer pair. Both monomers are similar in resonance, polarity, and steric characteristics. The acrylonitrile radical shows approximately equal reactivity with both monomers, and the methyl acrylate radical shows only a slight preference for reacting with acrylonitrile monomer. Many acrylonitrile monomer pairs fall into the nonideal category, eg, acrylonitrile—vinyl acetate. This is an example of a nonideality sometimes referred to as kinetic incompatibiUty. A third type of monomer pair is that which shows an alternating tendency. 

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). 

O.JVI. Scott Sons. The O.M. Scott Sons Co. (Scotts) has developed a series of coated products which utilize copolymer blends of vinyHdene chloride copolymerized with methyl methacrylates, acrylonitriles, methyl acrylates, and/or vinyHdene—vinyl chloride monomers. 

The Michael-type addition of maleic hydrazide and other pyridazinones to activated alkenes, such as methyl acrylate, acrylonitrile, methyl vinyl ketone and other a,/3-unsatu-rated carbonyl compounds, results in the formation of mono-lV-substituted products. 

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). 

In addition, Bamford, Jenkins and coworkers (19) previously reported on the behavior of occluded radicals in the heterogeneous polymerizations of acrylonitrile, methyl acrylate, methyl methacrylate and vinylidene chloride. From their electron spin resonance studies, they concluded that the degree of occlusion was ... 

The aziridine aldehyde 56 undergoes a facile Baylis-Hillman reaction with methyl or ethyl acrylate, acrylonitrile, methyl vinyl ketone, and vinyl sulfone [60]. The adducts 57 were obtained as mixtures of syn- and anfz-diastereomers. The synthetic utility of the Baylis-Hillman adducts was also investigated. With acetic anhydride in pyridine an SN2 -type substitution of the initially formed allylic acetate by an acetoxy group takes place to give product 58. Nucleophilic reactions of this product with, e. g., morpholine, thiol/Et3N, or sodium azide in DMSO resulted in an apparent displacement of the acetoxy group. Tentatively, this result may be explained by invoking the initial formation of an ionic intermediate 59, which is then followed by the reaction with the nucleophile as shown in Scheme 43. 

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. 

A number of examples have been reported documenting the use of palladium phosphine complexes as catalysts. The dialkyl species [PtL2R2] (L2 = dmpe, dppe, (PMe3)2 R = Me, CH2SiMe3) catalyze the reaction of [PhNH3]+ with activated alkenes (acrylonitrile, methyl acrylate, acrolein).176 Unfunctionalized alkenes prove unreactive. The reaction mechanism is believed to proceed via protonation of Pt-R by the ammonium salt (generating PhNH2 in turn) and the subsequent release of alkane to afford a vacant coordination site on the metal. Coordination of alkene then allows access into route A of the mechanism shown in Scheme 34. Protonation is also... 

For the addition of ethylene, EtOAc as solvent was particularly advantageous and gave 418 in 60% yield (Scheme 6.86). The monosubstituted ethylenes 1-hexene, vinylcyclohexane, allyltrimethylsilane, allyl alcohol, ethyl vinyl ether, vinyl acetate and N-vinyl-2-pyrrolidone furnished [2 + 2]-cycloadducts of the type 419 in yields of 54—100%. Mixtures of [2 + 2]-cycloadducts of the types 419 and 420 were formed with vinylcyclopropane, styrene and derivatives substituted at the phenyl group, acrylonitrile, methyl acrylate and phenyl vinyl thioether (yields of 56-76%), in which the diastereomers 419 predominated up to a ratio of 2.5 1 except in the case of the styrenes, where this ratio was 1 1. The Hammett p value for the addition of the styrenes to 417 turned out to be -0.54, suggesting that there is little charge separation in the transition state [155]. In the case of 6, the p value was determined as +0.79 (see Section 6.3.1) and indicates a slight polarization in the opposite direction. This astounding variety of substrates for 417 is contrasted by only a few monosubstituted ethylenes whose addition products with 417 could not be observed or were formed in only small amounts phenyl vinyl ether, vinyl bromide, (perfluorobutyl)-ethylene, phenyl vinyl sulfoxide and sulfone, methyl vinyl ketone and the vinylpyri-dines. 

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 ...

A similar method can be used for the addition of carbon tetrachloride to nonpolymerizable olefins (e.g., 1-octene, 2-octene, 1-butene, 2-butene) pure adducts are obtained in yields of over 90% if the components are allowed to react at 100° for 6 hours. Adducts of carbon tetrachloride with vinylic monomers (styrene, butadiene, acrylonitrile, methyl acrylate, etc.) can be prepared in good yields by substituting cupric chloride dihydrate in acetonitrile for ferric chloride hexahydrate and benzoin. 

Butadiene Styrene Methyl Methyacrylate Acrylonitrile Methyl Acrylate Vinyl Acetate Vinyl Chloride Q e... 

The question of regioselectivity arises when nonsymmetrically substituted alkenes, such as acrylates, acrylonitrile, (methyl)vinylketone, and cinnamic acid... 

Confirmation was provided by the observation that the species produced by the photolysis of two different carbene sources (88 and 89) in acetonitrile and by photolysis of the azirine 92 all had the same strong absorption band at 390 nm and all reacted with acrylonitrile at the same rate (fc=4.6 x 10 Af s" ). Rate constants were also measured for its reaction with a range of substituted alkenes, methanol and ferf-butanol. Laser flash photolysis work on the photolysis of 9-diazothioxan-threne in acetonitrile also produced a new band attributed the nitrile ylide 87 (47). The first alkyl-substituted example, acetonitrilio methylide (95), was produced in a similar way by the photolysis of diazomethane or diazirine in acetonitrile (20,21). This species showed a strong absorption at 280 nm and was trapped with a variety of electron-deficient olefinic and acetylenic dipolarophiles to give the expected cycloadducts (e.g., 96 and 97) in high yields. When diazomethane was used as the precursor, the reaction was carried out at —40 °C to minimize the rate of its cycloaddition to the dipolarophile. In the reactions with unsymmetrical dipolarophiles such as acrylonitrile, methyl acrylate, or methyl propiolate, the ratio of regioisomers was found to be 1 1. 

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). 

Activated olefins (acrylonitrile, methyl acrylate), and halides such as allyl bromide and ethyl bromoacetate were used as electrophiles. In nonpolar solvents, the enamines (126a) were alkylated with high enantioselectivity, but poor chemical yields. In polar solvents, the chemical yields were acceptable, the optical yields poor 148). A similar reaction sequence has been used successfully for the synthesis of (+)-mesembrine (133)149 >. 

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)... 

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