Hydroxylated nylons

We have recently developed a synthetic procedure for the preparation of polyhydroxypolyamides (hydroxylated nylons) of general structure I (1-2). While our synthetic method has some unique... 

Fleet et al. have described some oligomers of 0-protected-6-amino-6-deoxy-o-allonate [66] and o-galactonate [67], as intermediates in the preparation of poly-hydroxylated Nylon 6 analogs. 

L. Chen and D. E. Kiely, D-glucaric acid esters/lactones used in condensation polymerisation to produce hydroxylated nylons, a qualitative equilibrium study in acidic and basic conditions, J. Carbohydr. Chem., 13 (1994) 585-601. 

Our current major interest in aldaric acids is as monomers for polycondensation reactions with diamines to yield a broad class of polymers called polyhydroxypolyamides (PHPAs) or Hydroxylated Nylons (10). The original reports of examples of this class of polyamides were from the laboratory of N. Ogata and coworkers in Japan, beginning in the 1970s (11). More recent reports on these polymers have come from the laboratories of Hashimoto and coworkers (12) and those of author (13). Our general preparation of these polyamides, exemplified with a generic hexaric acid, is outlined in Figure 2. 

Kiely D.E., Chen. L., Lin T.-H., Hydroxylated nylons based on unprotected esterifled D-glucaric acid by simple condensation reactions, J. Am. Chem. Soc., 116,1994, 571-578. 

Chen. L., Kiely D.E., Synthesis of stereoregular head, tail hydroxylated nylons derived from D-glucose, J. Org. Chem., 61, 1996, 5847-5851. 

Hunter D.F.A., Fleet G.W.J., Towards hydroxylated nylon 6 Olygomers from a protected 6-amino-6-deoxy-D-aIlonate, Tetrahedron Asymm., 14, 2003, 3829-3831. 

Mayes B.A., Stetz R.J.E., Watterson M.P., Edwards A.A., Ansell C.W.G., Tranter G.E., Fleet G.W.J., Towards hydroxylated nylon 6 Linear and cyclic olygomers from a protected 6-tunino-6-deoxy-D-galactonate. A novel class of carbopep-toid-cyclodextrin (CPCD), Tetrahedron Asymm., 15, 2004,627-638. 

Castor is the only renewable vegetable oil resource (see Chemurgy) having a hydroxyl group stmcture and functionaHty that leads to diverse oleochemicals. In 1988, approximately 35,000 t/yr of castor oil were used to prepare raw materials for the manufacture of nylon-11. It is estimated that 40,000—45,000 t of... 

The first chemical agents used in composite fabrication were amino acids [179] for synthesizing Nylon 6. Other agents are also used in the synthesis of nanomaterials, however, the most popular are alkylammonium ions due to their ability to exchange ions located between the layers of the clay. In addition, silanes have been widely used due to their ability to react with the hydroxyl groups on the surface and edges of the clay layers. 

Caprolactam (5.68, Fig. 5.21) has a seven-membered lactam ring and is a major industrial compound in the production of Nylon , its polymer. This compound shows only moderate levels of toxicity in mice and rats when administered orally. The hydrolysis product 6-aminohexanoic acid (5.69) was a minor metabolite in rats [176]. Hydroxylation in the y-position to yield 5.70 without preliminary hydrolysis of the lactam linkage has been shown to be the major metabolic pathway. This metabolite hydrolyzes in urine to produce 6-amino-4-hydroxyhexanoic acid (5.71), which is in equilibrium with the corresponding lactone (5.72). 

Phenol, C6H5OH, is a benzene ring with a hydroxyl group, -OH, in place of a hydrogen. That makes it a member of the alcohol family. Most phenol is made by the oxidation route. At room temperature phenol is a solid but is corrosive like an acid. It is used to make phenolic resins and to make Bisphenol A (feed for epoxy and polycarbonate resins) and caprolactam (feed for Nylon 6). 

You can use analogies to put adipic acid in its right place. Acetic acid is the most important aliphatic monocarboxylic acid adipic is the most important aliphatic dicarboxylic acid. (You remember, of course, that carboxylic is the contraction for carbonyl and hydroxyl, -C-O and -OH, or together, -COOH. Right ) Also, adipic acid is to Nylon 66 what cumene is to phenol. About 95% of the adipic acid ends up as Nylon 66, which is used for tire cord, fibers, and engineering plastics. 

From non-aqueous solvents hydrogen bond adsorption of most proton donors occurs on inorganic oxides but on nylon and wool fibres only hydroxylic compounds are strongly adsorbed, either from non-aqueous solvents or in the vapouy phase. 

Little information is available upon hydrogen bond reactions in vapour phase adsorption, except in the important reactions of proteins and textile fibres with moisture, which have received widespread study. In these reactions substrate-water hydrogen bonds are undoubtedly responsible for the initial monolayer adsorption of water with increase in vapour pressure the adsorbed water condenses into multilayers by formation of water-water hydrogen bonds. Adsorption of organiq molecules of low molecular weight, in the vapour phase, on nylon or wool is considerably greater when they contain a hydroxylic group than when they do not [8] (Table 5), so that the hydroxy-compounds... 

Copolymers. Copolymers from mixtures of different bisphenols or from mixtures of dichlorosulfone and dichlorobenzophenone have been reported in the patent literature. Bifunctional hydroxyl-terminated polyethersulfone oligomers are prepared readily by the polyetherification reaction simply by providing a suitable excess of the bisphenol. Block copolymers are obtained by reaction of the oligomers with other polymers having end groups capable of reacting with the phenol. Multiblock copolymers of BPA-polysulfone with polysiloxane have been made in this way by reaction with dimethyl amino-terminated polydimethylsiloxane the products are effective impact modifiers for the polyethersulfone (79). Block copolymers with nylon-6 are obtained when chlorine-terminated oligomers, which are prepared by polyetherification with excess dihalosulfone, are used as initiators for polymerization of caprolactam (80). 

Amine and carboxyl functional coupling agents are recommended for both nylon and cellulosic materials. The amine groups of APDMSB can react with the carbonyl functionality and the carboxyl end groups of nylon, and with the hydroxyl groups of cellulose. The carboxyl groups of FA react with the nylon... 

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