Nitriles acrylonitrile

A high polymer resulting from the polymerisation of a mixture of two different monomers styrene-butadiene mbber, butyl (isoprene-isobutylene) mbber and nitrile (acrylonitrile-butadiene) mbber are typical copolymers. 

The synthesis of a-alkylglutaric acids (e.g. 2-propylglutaric acid, Expt 5.136), is conveniently achieved by allowing an alkylmalonic ester to react with the a, / -unsaturated nitrile, acrylonitrile, in thfe Michael manner and then subjecting the product to vigorous acidic hydrolysis. 

Propene, 2-methyl (isobutylene) Propenoic acid nitrile (acrylonitrile)... 

NITRILES Acrylonitrile. N-Amino-4,6-diphenylpyridone. n-Hexylamine. Hydroxyl-amine hydrochloride. lithium diethylamide-Hexamethylphosphoric triamide. Methyl carbazate. Phenyl isocyanate. p-Toluenesulfonic acid. Trifluoromethanesulfonic an-... 

Modified (or alloyed) phenolic Polyaromatics Polyester Polyurethane Anaerobic Cyanoacrylate Modified acrylic Neoprene (chloroprene) Nitriles (acrylonitrile-butadiene) Polysulfide Nitrile, vinyl, neoprene... 

The term acrylic apphes to a family of copolymers of monomers that are polymerized by a chain growth mechanism. Most often, the mechanism of polymerization is by free radical initiation. Other mechanisms of polymerization, such as ionic and group transfer polymerization, are possible but will not be discussed in this publication. For a description of other polymerization mechanisms, polymer textbooks are available (5,6). Technically, acrylic monomers are derivatives of acrylic or methacrylic acid. These derivatives are nonfunctional esters (methyl methacrylate, butyl acrylate, etc.), amides (acrylamide), nitrile (acrylonitrile), and esters that contain functional groups (hydroxyethyl acrylate, glycidyl methacrylate, dimethylaminoethyl acrylate). Other monomers that are not acryhc derivatives are often included as components of acryhc resins because they are readily copolymerized with the acryhc derivatives. Styrene is often used in significant quantities in acryhc copolymers. 

The addition of active methylene compounds (ethyl malonate, ethyl aoeto-acetate, ethyl plienylacetate, nltromethane, acrylonitrile, etc.) to the aP-double bond of a conjugated unsaturated ketone, ester or nitrile In the presence of a basic catalyst (sodium ethoxide, piperidine, diethylamiiie, etc.) is known as the Michael reaction or Michael addition. The reaction may be illustrated by the addition of ethyl malonate to ethyl fumarate in the presence of sodium ethoxide hydrolysis and decarboxylation of the addendum (ethyl propane-1 1 2 3-tetracarboxylate) yields trlcarballylic acid ... 

The mechanism of cyanoethylatlon is similar to that given in Section VI,21 for the Michael reaction. Acrylonitrile is the simplest ap-uiisaturated organic nitrile. 

Unsaturated nitriles are formed by the reaction of ethylene or propylene with Pd(CN)2[252]. The synthesis of unsaturated nitriles by a gas-phase reaction of alkenes. HCN, and oxygen was carried out by use of a Pd catalyst supported on active carbon. Acrylonitrile is formed from ethylene. Methacrylonitrile and crotononitrile are obtained from propylene[253]. Vinyl chloride is obtained in a high yield from ethylene and PdCl2 using highly polar solvents such as DMF. The reaction can be made catalytic by the use of chloranil[254]. 

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... 

Acrylonitrile-butadiene-styrene-poly(vinyl chlo- Nitrile resins... 

The principal monomer of nitrile resins is acrylonitrile (see Polyacrylonitrile ), which constitutes about 70% by weight of the polymer and provides the polymer with good gas barrier and chemical resistance properties. The remainder of the polymer is 20 to 30% methylacrylate (or styrene), with 0 to 10% butadiene to serve as an impact-modifying termonomer. 

Nitrile rubber (butadiene-acrylonitrile rubber) (also ... 

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 ... 

Even ia 1960 a catalytic route was considered the answer to the pollution problem and the by-product sulfate, but nearly ten years elapsed before a process was developed that could be used commercially. Some of the eadier attempts iacluded hydrolysis of acrylonitrile on a sulfonic acid ion-exchange resia (69). Manganese dioxide showed some catalytic activity (70), and copper ions present ia two different valence states were described as catalyticaHy active (71), but copper metal by itself was not active. A variety of catalysts, such as Umshibara or I Jllmann copper and nickel, were used for the hydrolysis of aromatic nitriles, but aUphatic nitriles did not react usiag these catalysts (72). Beginning ia 1971 a series of patents were issued to The Dow Chemical Company (73) describiag the use of copper metal catalysis. Full-scale production was achieved the same year. A solution of acrylonitrile ia water was passed over a fixed bed of copper catalyst at 85°C, which produced a solution of acrylamide ia water with very high conversions and selectivities to acrylamide. 

The heat of hydration is approximately —70 kj /mol (—17 kcal/mol). This process usually produces no waste streams, but if the acrylonitrile feed contains other nitrile impurities, they will be converted to the corresponding amides. Another reaction that is prone to take place is the hydrolysis of acrylamide to acryhc acid and ammonia. However, this impurity can usually be kept at very low concentrations. American Cyanamid uses a similar process ia both the United States and Europe, which provides for their own needs and for sales to the merchant market. 

Nitrile mbber finds broad application in industry because of its excellent resistance to oil and chemicals, its good flexibility at low temperatures, high abrasion and heat resistance (up to 120°C), and good mechanical properties. Nitrile mbber consists of butadiene—acrylonitrile copolymers with an acrylonitrile content ranging from 15 to 45% (see Elastomers, SYNTHETIC, NITRILE RUBBER). In addition to the traditional applications of nitrile mbber for hoses, gaskets, seals, and oil well equipment, new applications have emerged with the development of nitrile mbber blends with poly(vinyl chloride) (PVC). These blends combine the chemical resistance and low temperature flexibility characteristics of nitrile mbber with the stability and ozone resistance of PVC. This has greatly expanded the use of nitrile mbber in outdoor applications for hoses, belts, and cable jackets, where ozone resistance is necessary. 

Acrylonitrile (AN), C H N, first became an important polymeric building block in the 1940s. Although it had been discovered in 1893 (1), its unique properties were not realized until the development of nitrile mbbers during World War II (see Elastomers, synthetic, nitrile rubber) and the discovery of solvents for the homopolymer with resultant fiber appHcations (see Fibers, acrylic) for textiles and carbon fibers. As a comonomer, acrylonitrile (qv) contributes hardness, rigidity, solvent and light resistance, gas impermeabiUty, and the abiUty to orient. These properties have led to many copolymer apphcation developments since 1950. 

This tendency is related to the polarization properties of the monomer substituents (42). Monomers that are dissimilar in polarity tend to form alternating monomer sequences in the polymer chain. An example is the monomer pair acrylonitrile—styrene. Styrene, with its pendent phenyl group, has a relatively electronegative double bond whereas acrylonitrile, with its electron-withdrawing nitrile group, tends to be electropositive. 

Nitrile Rubber. Vulcanized mbber sheets of NBR and montmorillonite clay intercalated with Hycar ATBN, a butadiene acrylonitrile copolymer have been synthesized (36). These mbber hybrids show enhanced reinforcement (up to four times as large) relative to both carbon black-reinforced and pure NBR. Additionally, these hybrids are more easily processed than carbon black-filled mbbers. 

Reactions. The chemical properties of cyanoacetates ate quite similar to those of the malonates. The carbonyl activity of the ester function is increased by the cyano group s tendency to withdraw electrons. Therefore, amidation with ammonia [7664-41-7] to cyanoacetamide [107-91-5] (55) or with urea to cyanoacetylurea [448-98-2] (56) proceeds very easily. An interesting reaction of cyanoacetic acid is the Knoevenagel condensation with aldehydes followed by decarboxylation which leads to substituted acrylonitriles (57) such as (29), or with ketones followed by decarboxylation with a shift of the double bond to give P,y-unsaturated nitriles (58) such as (30) when cyclohexanone [108-94-1] is used. 

Ring Synthesis From Nonheterocyclic Compounds. These methods may be further classified based on the number of bonds formed during the pyridine ring formation. Synthesis of a-picoline (2) from 5-oxohexanenitrile is a one-bond formation reaction (eq. 16) (49). The nitrile is obtained by reaction between acetone and acrylonitrile (50). If both reaction steps are considered together, the synthesis must be considered a two-bond forming one, ie, formation of (2) from acetone and acrylonitrile in a single step comes under the category of two-bond formation reaction. 

BP. These nitrile alloy membranes are compounded from PVC, flexibilized by the addition of butadiene—acrylonitrile copolymers, PVC, and other proprietary ingredients. Typically reinforced with polyester scrim, NBP membranes are 1 mm thick and have a width of 1.5 m. They ate ptedominandy used in mechanically fastened roofing systems. NBP membranes exhibit excellent teat and puncture resistance as well as good weatherabihty, and remain flexible at low temperatures. They ate resistant to most chemicals but ate sensitive to aromatic hydrocarbons. The sheet is usually offered in light colors. The physical characteristics of NBP membranes have been described (15). 

Nitrile Rubber. Nitrile mbbers are made by the emulsion copolymerization of acrylonitrile (9—50%) and butadiene (6) and designated NBR. The ratio of acrylonitrile (ACN) to butadiene has a direct effect on the properties on the nature of the polymers. As the ACN content increases, the oil resistance of the polymer increases (7). As the butadiene content increases, the low temperature properties of the polymer are improved (see Elastomers, SYNTHETIC-NITRILE RUBBER). 

---