Polyacrylonitrile hydrolysis

The second group includes SAHs obtained by radical grafting of acrylonitrile (AN) on natural polymers, mostly starch, under the action of cerium initiators [43 -46, 50, 51], The proper crosslinked hydrophilic polymer is formed at the stage of alkali hydrolysis of grafted polyacrylonitrile (PAN), the final characteristics depending on many factors, in particular the sort of starch [46], the methods of its preparation [51], the component ratio, etc. The nature of starch is exhibited through... 

There are two pathways for the degradation of nitriles (a) direct formation of carboxylic acids by the activity of a nitrilase, for example, in Bacillus sp. strain OxB-1 and P. syringae B728a (b) hydration to amides followed by hydrolysis, for example, in P. chlororaphis (Oinuma et al. 2003). The monomer acrylonitrile occurs in wastewater from the production of polyacrylonitrile (PAN), and is hydrolyzed by bacteria to acrylate by the combined activity of a nitrilase (hydratase) and an amidase. Acrylate is then degraded by hydration to either lactate or P-hydroxypropionate. The nitrilase or amidase is also capable of hydrolyzing the nitrile group in a number of other nitriles (Robertson et al. 2004) including PAN (Tauber et al. 2000). 

Production of hydrogels by chemical conversion uses chemical reactions to convert one type of gel to another. This can involve the conversion of a nonhydrogel to a hydrogel or the conversion of one type of hydrogel to another. Examples of the former include the hydrolysis of polyacrylonitrile to polyacrylamide or of poly(vinyl acetate) to poly(vinyl alcohol) an example of the latter... 

Fischer-Colbrie, G., Matama, T., Heumann, S. et al. (2007) Surface hydrolysis of polyacrylonitrile with nitrile hydrolysing enzymes from Micrococcus luteus BST20. Journal of Biotechnology, 129, 62-68. 

Keywords Cutinase Polyacrylonitrile Polyamide Polyethyleneterphthalate Surface hydrolysis... 

Fischer-Colbrie G, Matama T, Heumann S et al (2007) Surface hydrolysis of polyacrylonitrile with a nitrilase of a new strain of Micrococcus luteus. J Biotechnol 128 849-857... 

Chapter 5 shows that the application of hydrolytic enzymes is a powerful yet mild strategy to directly improve polymer surface properties (i.e. hydrophilicity) or activate materials for further processing. The surface hydrolysis of polyamides (PA), polyethyleneterphthalates (PET) and polyacrylonitriles (PAN) is discussed, as well as the mechanistic details on the enzymatic surface hydrolysis. The mechanistic data, combined with advances in structural and molecular biology, help to explain different activities of closely related enzymes on polymer surfaces. 

In streptocyanine dyes both ends of the methine chain are joined directly to nitrogen atoms, and a double enamine structure is thus present. The dyes are extremely susceptible to hydrolysis, particularly if they contain secondary nitrogen atoms. Stable dyes are obtained if the nitrogen is part of a heterocyclic ring system. Streptocyanine dyes are brilliant yellow dyes that dye polyacrylonitrile and acid-modified polyamide fibers with outstanding lightfastness [1],... 

Hydrolysis of Bamboo-Polyacrylonitrile Copolymer. In order to isolate the polymer branches of the graft copolymers and to check the accuracy of the grafting percentages... 

Thus polystyryl carbanions and polyacrylonitrile carbanions prepared by anionic polymerization were reacted with cellulose acetate or tosylated cellulose acetate in tetrahydrofuran under homogenous reaction conditions. The carbanions displaced the acetate groups or the tosylate groups in a S v2-type nucleophilic displacement reaction to give CA-g-PS and CA-g-PAN. Mild hydrolysis to remove the acetate/tosylate groups furnishes the pure cellulose-g-polystyrene (Figure 3). 

Polymers with pendant groups that are derivatives of carboxylic acid can he hydrolyzed to yield poly(acrylic acid). This includes polymers like polyacrylamide, polyacrylonitrile, and polyacrylates. When heated, poly(acrylic acid) form polymeric anhydrides, which undergo typical reactions of anhydrides, such as hydrolysis, alcoholysis, and amidation. 

Limited surface hydrolysis ofpoly(alkyleneterephthalate)s (PAT), polyamides (PA) and polyacrylonitriles (PAN) by enzymes increases their hydrophilicity which is... 

The enantioselective hydrolysis is carried out in an organic-aqueous two-phase reactor (toluene/water), where the phase contact is established by a hydrophilic hollow-fiber membrane (polyacrylonitrile). The lipase is immobilized onto a spongy layer by pressurized adsorption. The productivity is about 40 kg trans-(2R,3S)-(4-methoxyphenyl) glycidic acid methyl ester m-2 a-1. This process has been operated since 1993. 

Polyacrylonitrile (M = 2700) could be obtained (after hydrolysis) by interaction of Dyl2 with acrylonitrile (Balashova et al., 2004). 

Benzonitrile acts in a similar way to form benzoic acid but requires sulfuric acid in the reacting mixture. Nicotinic acid amide (nicotinamide) has been prepared by the mild hydrolysis of 3-cyanopyridine, and acrylamide by the partial hydrolysis of acrylonitrile. Acrylonitrile may also be hydrolyzed to acrylic acid with mineral acids or with alkalies. Polyacrylonitrile is partially converted to the amide by nitric acid, and the nitrile oups of a number of polymers and copolymers have been hydrolyzed to amide and carboxylic acid groups to produce water-soluble polyelectrolytes. Isooyanides are stable toward alkalies but hydrolyze in the presence of acids to form an acid and an amine ... 

An enzymatic production process for Diltiazem (54), a coronary vasodilator and calcium channel blocker, was started in 1993 by Tanabe Seiyaku, Japan [7, 77]. The epoxide (2i, 3S)-52 is a key intermediate in this synthesis (Scheme 17) and can be produced via asymmetric hydrolysis of rac-52 catalyzed by Serratia marescens lipase immobilized on spongy layers. The whole process takes place in a polyacrylonitrile hollow fiber membrane reactor and produces (2i, 3S)-52 in yields of 40-45%. The hydrolyzed product (2S,3i )-53 is not stable under the prevailing reaction conditions and decarboxylates to aldehyde 55, a strong enzyme deactivator. The aldehyde needs therefore to be removed, which is achieved by continuous filtration of its bisulfite adduct 56. Using this enzymatic process it was possible to bring down the number of required steps en route to 54 from nine to five. This process is also carried out by other companies (e.g., DSM) with a worldwide annual production of 1001. 

Polyacrylonitrile (PAN) has been used in the preparation of UP membranes for a long time [82, 83] due to its superior resistance to hydrolysis and oxidation. PAN is highly crystalline and relatively hydrophilic and is usually copolymerized with more hydrophilic monomers to improve processability and to make it less brittle. Hollow fibers can be prepared from PAN dissolved in nitric acid [84]. Preparation of PAN membranes by phase inversion from solutions in DMAC, DMF or NMP is also possible. An example is shown in Fig. 4.4. A Sumitomo patent [85] discloses the preparation of membranes from copolymers containing 89% acrylonitrile and 11% ethyl acrylate dissolved in DMF and formamide and coagulated in water. A microporous membrane is obtained. In order to make the membranes suitable for reverse osmosis, they were submitted to a plasma treatment in the presence of 4-vinyl pyridine. 

Definition Copolymer formed by the controlled hydrolysis of polyacrylonitrile Uses Film-former in cosmetics emulsifier, thickener, gellant, film-former for pharmaceuticals... 

Definition Polymer formed from controlled hydrolysis of polyacrylonitrile neutralized by ammonia... 

Trade Name Synonyms Lamepon PA-TR [Cognis/Care Chems.] Lamepon PA-TR/NP t[Cognis/Care Chems.] Lexein A-520 t[lnolex http //www.inolex.com], Uniprolam PAJR [Universal Preserv-A-Chem http //WWW. upichem. com] TEA-acrylates/acrylonitrogens copolymer Definition Polymer formed from the controlled hydrolysis of polyacrylonitrile neutralized by triethanolamine... 

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