Ordered polyamide

Our group has initiated a synthesis of ordered polymer from nonsymmetric monomers by direct polycondensation. In the previous papers, we reported a successful synthesis of ordered polyamides (head-to-head or tail-to-tail) from a synunetric monomer and a nonsynunetric monomer, (7,2), and ordered polyamides (head-to-tail) from a synunetric monomer and a nonsynunetric monomer or a pair of two synunetric monomers (3). 

Synthesis of Authentic Ordered Polyamide (10a). In order to clarify the structure of ordered polymer, N J4 -bis(4-aininobenzoyl)i ophtfaalohydrazide (8) and di(4-nitrophenyI) 33 -(thiodi-p pbenylenethio)dipropanoate (9) were prepared by the condensation of isophthalic acid with 4-aminophenylhydrazide in the presence of 1, and the addition reaction of 4-nitrophenyl acrylate with 4,4 -thiobisbenzenethiol, respectively (eq. 4,5). 

The polyamides poly(hexamethylene sebacamide) and poly(hexamethylene adipamide) are also widely known as nylon-6,10 and nylon-6,6, respectively. The numbers following the word nylon indicate the number of carbon atoms in the diamine and dicarboxylic acid, in that order. On the basis of this same system, poly (e-caprolactam) is also known as nylon-6. 

The polyamides are soluble in high strength sulfuric acid or in mixtures of hexamethylphosphoramide, /V, /V- dim ethyl acetam i de and LiCl. In the latter, compHcated relationships exist between solvent composition and the temperature at which the Hquid crystal phase forms. The polyamide solutions show an abmpt decrease in viscosity which is characteristic of mesophase formation when a critical volume fraction of polymer ( ) is exceeded. The viscosity may decrease, however, in the Hquid crystal phase if the molecular ordering allows the rod-shaped entities to gHde past one another more easily despite the higher concentration. The Hquid crystal phase is optically anisotropic and the texture is nematic. The nematic texture can be transformed to a chiral nematic texture by adding chiral species as a dopant or incorporating a chiral unit in the main chain as a copolymer (30). 

Similady, hquid-crystal polymers exhibit considerable order in the hquid state, either in solution (lyotropic) or melt (thermotropic). When crystallized from solution or melt, they have a high degree of extended-chain crystallinity, and thus have superior mechanical properties. Kevlar (Du Pont) is an aromatic polyamide (atamid) with the repeating unit designated as (2). It is spun into... 

Molded polyamide surfaces can be hardened by grafting with Ai,Ai-diallylacrylamide [3085-68-5] monomer under exposure to electron beam (159). AijAZ-DiaHyltartardiamide [58477-85-3] is a cross-linking agent for acrylamide reversible gels in electrophoresis. Such gels can be dissolved by a dilute periodic acid solution in order to recover protein fractions. 

In order to become useful dmg delivery devices, biodegradable polymers must be formable into desired shapes of appropriate size, have adequate dimensional stability and appropriate strength-loss characteristics, be completely biodegradable, and be sterilizahle (70). The polymers most often studied for biodegradable dmg delivery applications are carboxylic acid derivatives such as polyamides poly(a-hydroxy acids) such as poly(lactic acid) [26100-51-6] and poly(glycolic acid) [26124-68-5], cross-linked polyesters poly(orthoesters) poly anhydrides and poly(alkyl 2-cyanoacrylates). The relative stabiUty of hydrolytically labile linkages ia these polymers (70) is as follows ... 

Since large tonnage production is desirable in order to minimise the cost of a polyamide and since the consumption of nylons as plastics materials remains rather small, it is important that any new materials introduced should also have a large outlet as a fibre. There are a number of polyamides in addition to those already mentioned that could well be very useful plastics materials but which would be uneconomical for all but a few applications if they were dependent on a limited outlet in the sphere of plastics. Both nylon 7 and nylon 9 are such examples but their availability as plastics is likely to occur only if they become established fibre-forming polymers. This in turn will depend on the economics of the telomerisation process and the ability to find outlets for the telomers produced other than those required for making the polyamides. 

Polyamides such as nylon 6, nylon 66, nylon 610, nylon 11 and nylon 12 exhibit properties which are largely due to their high molecular order and the high degree of interchain attraction which is a result of their ability to undergo hydrogen bonding. 

Linear step-growth polymerizations require exceptionally pure monomers in order to ensure 1 1 stoichiometry for mutually reactive functional groups. For example, the synthesis of high-molecular-weight polyamides requires a 1 1 molar ratio of a dicarboxylic acid and a diamine. In many commercial processes, the polymerization process is designed to ensure perfect functional group stoichiometry. For example, commercial polyesterification processes often utilize dimethyl terephthalate (DMT) in the presence of excess ethylene glycol (EG) to form the stoichiometric precursor bis(hydroxyethyl)terephthalate (BHET) in situ. 

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