1,2-Diamines from 1.2-diols

A range of bis- and tris-spirocyclic cyclotriphosphazenes 182-187 containing bi-2-napthoxy, 2,2 -biphenoxy, 2,2-dimethyl-1,3-propane diamino, and 2,2-dimethyl-1,3-propane dioxy ligands have been prepared from the appropriate diamines and diols <2004POL979>. 

The common condensation polymers and the reactions by which they are formed are shown in Table 1-1. It should be noted from Table 1-1 that for many of the condensation polymers there are different combinations of reactants that can be employed for their synthesis. Thus polyamides can be synthesized by the reactions of diamines with diacids or diacyl chlorides and by the self-condensation of amino acids. Similarly, polyesters can be synthesized from diols by esterification with diacids or ester interchange with diesters. 

Dimethy 1-4,4 -diamino-1,1 -biphenyl dihydrochloride was obtained from Professor Lorraine Deck at the University of New Mexico and used as received. Maleic anhydride was obtained from Eastman Kodak and p-aminobenzoic was obtained from National Starch. The other anhydrides, diols, and reagents were purchased from Aldrich Chemical. All reagents were used without further purification. The monomers were synthesized via a Schotten-Baumann type procedure using the appropriate acid chloride endcap and diamines or diols. Triethylamine was used as a scavenger for HC1. The monomers were recrystallized from appropriate solvents in yields of approximately 70%. 

The preparation of polyamides having metallocenes incorporated into the backbone can be achieved by the use of bifunctional ferrocene derivatives, such as diacid chlorides or diamines. In the following, a few examples of such reactions are presented. In the early 1960s Knobloch and Rauscher reported the preparation of polyamides and polyesters by the reaction of 1,1 ferrocenyldicarbonyl chloride 14 with several diamines and diols by interfacial polycondensation.80 The synthesis of elastomeric polyamides 54a, Mn = 10,000-18,000) in high yields was reported by Rausch and co-workers from 1,1 -bis((3-aminoethyl)ferrocene 53 and diacid chlorides (Scheme 12.11). The reaction with bis-isocyanates allows the formation of ferrocene-containing polyureas 54b. 

The tin template cyclization reaction is useful for the preparation of ma-crocyclic compounds from diols, dithiols, and diamines (Leygue et al., 1988). 

AjAjA jA -Tetrasubstituted diamines are obtained from diol bissulfonates and secondary amines 851... 

J/n < 6,000). Often, no analytical data or structural characterization was provided. Room-temperature interfacial polycondensation methods were also investigated as a convenient alternative to classical polycondensations. Such methods were first reported for the preparation of polyamides and polyesters from the reaction of l,l -ferrocenyldi-carbonyl chloride with several diamines and diols. The synthesis of polyurethanes using this technique was also reported and involved the condensation of l,T-ferrocenedimethanol and l,T-bis(dihydroxyethyl)ferrocene with diisocyanates. Once again, however, these polymers possessed low molecular weights.The early research in these areas has been summarized and critically reviewed and will not be discussed further here. ... 

In the early days of macromolecular chemistry, synthetic polymers were simply labeled according to the monomer from which they were prepared. Thus, ethylene polymers became poly(ethylenes), styrene polymers became poly(styrenes), and those from lactams became poly (lactams). In other cases, the choice of name was provided by a characteristic group occurring in the final polymer. Thus, polymers from diamines and dicarboxylic acids were called polyamides, and those from diols and dicarboxylic acids were called polyesters. This phenomenological nomenclature fails, of necessity, when more than one kind of monomeric unit can be formed from a given monomer. 

Amide formation plays a very important role in chemical synthesis [1, 46]. Preparation of amides under neutral conditions and without generation of waste is a challenging goal [46-48]. Applying our pyridine-based ruthenium pincer complexes as catalysts, amides were synthesized directly from amines and alcohols or esters polyamides were obtained from diols and diamines, as delineated in this section. 

The kinetic treatment of polyreactions is greatly simplified by applying the principle of equal chemical reactivity. This principle assumes that the reactivity of a chemical group is independent of the size of the molecule to which it is attached. This postulated independence of rate constant from molecular size is already achieved at low degrees of polymerization, as can be seen, for example, by comparing the rate constants for the hydrolytic degradation of oligopolysaccharides (Table 15-5). Confirmation of the principle of equal chemical reactivity is also obtained from the polycondensation of dicarboxylic acids with diamines or diols and from free radical polymerizations. 

Fig. 3.13. DSC scans of the diamine and diol chain-extended polyurethane elastomers (arrow designates the position of the transition) (from Barikani,...

The use of oil/water (OAV) emulsions has also been employed to fabricate PU NPs [162-165]. In this method, the diisocyanate (IPDI) is first dissolved in an oil/ surfactant mixture (90/10, saturated medium chain triglyceride/polysorbate 80 [polyoxyethylene 20-sorbitan monooleate]). Addition of the aqueous phase with PEG 400 (diamine or diol) to the 0/S mixture in dropwise fashion (to obtain 90% aqueous component) occurs under mechanical stirring to obtain nanoemulsions, followed by heating to 70 °C to allow polymerization and achieve PU or PU urea NPs, which can be isolated by ultracentrifugation [165]. This method works by having IPDI present in the core of oil nanodroplets in the 0/W nanoemulsion, which react with the diols or diamines at the surface of the oil droplet, resulting in the formation of the NPs with a size distribution from 40 to lOOnm. 

Cross-linking can be done by various techniques depending on the chemical composition of the polymer. Thus, if the polymer contains C=C unsaturation, e.g. in polydienes, natural rubber, polyisobutylenes (from copolymerized isoprene), then reaction with sulphur forms —S—S— links. With polysiloxanes or EP rubbers (no C=C) then peroxides are used. With fluorocarbon elastomers, e.g. Viton (a copolymer of vinylidene difluoride and hexafluoropropylene), diamines are used which form H-bonded cross-links. With polyurethanes (formed from diols and di-isocyanates) a controlled number (low) of cross-links are formed during the polymerization by the addition of triols. 

Cleavage of ethylene derivs. to alcohols and amines Diols and diamines from cyclic ethylene derivs. 

Gnanaprakasam B, Balaraman E, Gunanathan C, Milstein D (2012) Synthesis of polyamides from diols and diamines with liberation of H2. J Poly Sci Part A Polymer Chem 50 1755... 

---