Acrylonitrile preparation

The death of a 10-year-old girl following dermal exposure to acrylonitrile was reported by Lorz (1950). An acrylonitrile preparation had been applied to the scalp of the child as a treatment for head lice. The child experienced nausea, headache and dizziness. Death occurred 4 hours after application. The concentration was not specified in this case report. 

Suta, B.E. (1979) Assessment ofHimian Exposures to Atmospheric Acrylonitrile, Prepared for USEPA, Contract No 68-02-2835. Task 20, Research Triangle Park, NC, SRI International... 

The graft polybutadiene containing both styrene and acrylonitrile prepared in a separate experiment was isolated by a double precipitation. The experimental value for the degree of grafting was calculated on the basis of the trans isomer of polybutadiene (Figure 17). Except for two fractions, the styrene contents are within the shaded band. We note that both the styrene and the acrylonitrile contents increase slightly. This phenomenon might be caused by the polymerization temperature which was lower than in the previous two experiments (100°C. instead of 110°C.). 

Table 6.7 Experimental values of composition and microstructure parameters of copolymer of styrene with acrylonitrile prepared in bulk at T = 60 °C. Composition was determined by two techniques NMR-spectroscopy and elementary nitrogen analysis [215, 282]. Characteristic coefficients were calculated via Eqs. (6.15), (6,2) according to the experimental data adduced in Refs. [215, 282]... 

In Figure 11.1 the MMCCD of a commercial copolymer of styroie and acrylonitrile prepared by suspension copolymerization is shown, and was obtained by a combination of GPC and HPLC measurements [116]. 

K. R. Sharma, First Order Markov Model Representation of Chain Seqnence Distribution of Alphamethylstyrene Acrylonitrile Prepared by Reversible Free Radical Polymerization, 229th ACS National Meeting, San Diego, CA, March 2005. 

The third of the potential feedstoeks for the manufacture of adiponitrile is acrylonitrile, prepared by the ammoxidation of propylene. The only route to... 

The acylpalladium complex formed from acyl halides undergoes intramolecular alkene insertion. 2,5-Hexadienoyl chloride (894) is converted into phenol in its attempted Rosenmund reduction[759]. The reaction is explained by the oxidative addition, intramolecular alkene insertion to generate 895, and / -elimination. Chloroformate will be a useful compound for the preparation of a, /3-unsaturated esters if its oxidative addition and alkene insertion are possible. An intramolecular version is known, namely homoallylic chloroformates are converted into a-methylene-7-butyrolactones in moderate yields[760]. As another example, the homoallylic chloroformamide 896 is converted into the q-methylene- -butyrolactams 897 and 898[761]. An intermolecular version of alkene insertion into acyl chlorides is known only with bridgehead acid chlorides. Adamantanecarbonyl chloride (899) reacts with acrylonitrile to give the unsaturated ketone 900[762],... 

PROPENE The major use of propene is in the produc tion of polypropylene Two other propene derived organic chemicals acrylonitrile and propylene oxide are also starting materials for polymer synthesis Acrylonitrile is used to make acrylic fibers (see Table 6 5) and propylene oxide is one component in the preparation of polyurethane polymers Cumene itself has no direct uses but rather serves as the starting material in a process that yields two valuable indus trial chemicals acetone and phenol... 

An important nitrile is acrylonitrile H2C=CHCN It is prepared industrially from propene ammonia and oxygen m the presence of a special catalyst Polymers of acryl omtrile have many applications the most prominent being their use m the preparation of acrylic fibers... 

The physical properties of cyanoacetic acid [372-09-8] and two of its ester derivatives are Hsted ia Table 11 (82). The parent acid is a strong organic acid with a dissociation constant at 25°C of 3.36 x 10. It is prepared by the reaction of chloroacetic acid with sodium cyanide. It is hygroscopic and highly soluble ia alcohols and diethyl ether but iasoluble ia both aromatic and aUphatic hydrocarbons. It undergoes typical nitrile and acid reactions but the presence of the nitrile and the carboxyUc acid on the same carbon cause the hydrogens on C-2 to be readily replaced. The resulting malonic acid derivative decarboxylates to a substituted acrylonitrile ... 

Acrylic Acid, Acrylates, and Acrylonitrile. Acryhc acid [79-10-7], and acrylates were once prepared by reaction of acetylene and... 

A number of methods such as ultrasonics (137), radiation (138), and chemical techniques (139—141), including the use of polymer radicals, polymer ions, and organometaUic initiators, have been used to prepare acrylonitrile block copolymers (142). Block comonomers include styrene, methyl acrylate, methyl methacrylate, vinyl chloride, vinyl acetate, 4-vinylpyridine, acryUc acid, and -butyl isocyanate. 

Aminoalkoxy pentaerythritols are obtained by reduction of the cyanoethoxy species obtained from the reaction between acrylonitrile, pentaerythritol, and lithium hydroxide in aqueous solution. Hydrogen in toluene over a mthenium catalyst in the presence of ammonia is used (34). The corresponding aminophenoxyalkyl derivatives of pentaerythritol and trimethyl olpropane can also be prepared (35). 

Acrylonitrile and its comonomers can be polymerized by any of the weU-known free-radical methods. Bulk polymerization is the most fundamental of these, but its commercial use is limited by its autocatalytic nature. Aqueous dispersion polymerization is the most common commercial method, whereas solution polymerization is used ia cases where the spinning dope can be prepared directly from the polymerization reaction product. Emulsion polymerization is used primarily for modacryhc compositions where a high level of a water-iasoluble monomer is used or where the monomer mixture is relatively slow reacting. 

A significant development ia trifluoromethylpyridine synthesis strategy is the use of fluoriaated aUphatic feedstocks for the ring-constmction sequence. Examples iaclude the manufacture of the herbicide dithiopyr, utilising ethyl 4,4,4-trifluoroacetoacetate [372-31-6] CF2COCH2COOC2H (436,437). 2,3-Dichloro-5-trifluoromethylpyridine [69045-84-7], a precursor to several crop-protection chemicals (see Table 15), can be prepared by conversion of l,l,l-trichloro-2,2,2-trifluoroethane [354-58-5], CF CCl, to 2,2-dichloro-3,3,3-trifluoropropionaldehyde [82107-24-2], CF2CCI2CHO, followed by cycUzation with acrylonitrile [107-13-1] (415). 

Copolymers of VF and a wide variety of other monomers have been prepared (6,41—48). The high energy of the propagating vinyl fluoride radical strongly influences the course of these polymerizations. VF incorporates well with other monomers that do not produce stable free radicals, such as ethylene and vinyl acetate, but is sparingly incorporated with more stable radicals such as acrylonitrile [107-13-1] and vinyl chloride. An Alfrey-Price value of 0.010 0.005 and an e value of 0.8 0.2 have been determined (49). The low value of is consistent with titde resonance stability and the e value is suggestive of an electron-rich monomer. 

HydroxyethyUiydrazine (11) is a plant growth regulator. It is also used to make a coccidiostat, furazoHdone, and has been proposed, as has (14), as a stabilizer in the polymerization of acrylonitrile (72,73). With excess epoxide, polysubstitution occurs and polyol chains can form to give poly(hydroxyaLkyl) hydrazines which have been patented for the preparation of cellular polyurethanes (74) and as corrosion inhibitors for hydrauHc fluids (qv) (75). DialkyUiydrazines, R2NNH2, and alkylene oxides form the very reactive amineimines (15) which react further with esters to yield aminimides (16) ... 

MAA and MMA may also be prepared via the ammoxidation of isobutylene to give meth acrylonitrile as the key intermediate. A mixture of isobutjiene, ammonia, and air are passed over a complex mixed metal oxide catalyst at elevated temperatures to give a 70—80% yield of methacrylonitrile. Suitable catalysts often include mixtures of molybdenum, bismuth, iron, and antimony, in addition to a noble metal (131—133). The meth acrylonitrile formed may then be hydrolyzed to methacrjiamide by treatment with one equivalent of sulfuric acid. The methacrjiamide can be esterified to MMA or hydrolyzed to MAA under conditions similar to those employed in the ACH process. The relatively modest yields obtainable in the ammoxidation reaction and the generation of a considerable acid waste stream combine to make this process economically less desirable than the ACH or C-4 oxidation to methacrolein processes. 

Such copolymers of oxygen have been prepared from styrene, a-methylstyrene, indene, ketenes, butadiene, isoprene, l,l-diphen5iethylene, methyl methacrjiate, methyl acrylate, acrylonitrile, and vinyl chloride (44,66,109). 1,3-Dienes, such as butadiene, yield randomly distributed 1,2- and 1,4-copolymers. Oxygen pressure and olefin stmcture are important factors in these reactions for example, other products, eg, carbonyl compounds, epoxides, etc, can form at low oxygen pressures. Polymers possessing dialkyl peroxide moieties in the polymer backbone have also been prepared by base-catalyzed condensations of di(hydroxy-/ f2 -alkyl) peroxides with dibasic acid chlorides or bis(chloroformates) (110). 

Fig. 10. Preparation and morphology of toughened PVC (a) secondary PVC grain (50—250 flm) (b) modified PVC with coherent primary grain (ca 1 -lm) (220). CPE = chlorinated polyethylene EVA = ethylene—vinyl acetate copolymers ABS = acrylonitrile—butadiene—styrene MBS = methyl...

CH3)2CH0H + CH2=C=0 CH3C00CH(CH3)2 and the Ritter reaction to prepare A/-isopropylacrylamide [2210-25-5] from acrylonitrile [107-13-1] and isopropyl alcohol ... 

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. 

Styrene Copolymers. Acrylonitrile, butadiene, a-methylstyrene, acryUc acid, and maleic anhydride have been copolymerized with styrene to yield commercially significant copolymers. Acrylonitrile copolymer with styrene (SAN), the largest-volume styrenic copolymer, is used in appHcations requiring increased strength and chemical resistance over PS. Most of these polymers have been prepared at the cross-over or azeotropic composition, which is ca 24 wt % acrylonitrile (see Acrylonithile polya rs Copolyp rs). 

Copolymers are typically manufactured using weU-mixed continuous-stirred tank reactor (cstr) processes, where the lack of composition drift does not cause loss of transparency. SAN copolymers prepared in batch or continuous plug-flow processes, on the other hand, are typically hazy on account of composition drift. SAN copolymers with as Httle as 4% by wt difference in acrylonitrile composition are immiscible (44). SAN is extremely incompatible with PS as Httle as 50 ppm of PS contamination in SAN causes haze. Copolymers with over 30 wt % acrylonitrile are available and have good barrier properties. If the acrylonitrile content of the copolymer is increased to >40 wt %, the copolymer becomes ductile. These copolymers also constitute the rigid matrix phase of the ABS engineering plastics. 

Amide-Based Sulfonic Acids. The most important amide-based sulfonic acids are the alkenylarnidoalkanesulfoiiic acids. These materials have been extensively described ia the Hterature. A variety of examples are given ia Table 5. Acrylarnidoalkanesulfoiiic acids are typically prepared usiag technology originally disclosed by Lubrizol Corporation ia 1970 (80). The chemistry iavolves an initial reaction of an olefin, which contains at least one aHyhc proton, with an acyl hydrogen sulfate source, to produce a sulfonated intermediate. This intermediate subsequendy reacts with water, acrylonitrile, and sulfuric acid. 

Michael-Type Additions. Michael additions are generally used to prepare methyl 3-mercaptopropionate (eq. 10) and mercaptopropionitrile (eq. 11) by the reaction of methyl acrylate or acrylonitrile and hydrogen sulfide using a basic catalyst. This reaction proceeds as shown ... 

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