Polyureas synthesis methods

The molecular imprinting method can be used to synthesize enantioselective solid materials for asymmetric organic synthesis. The first attempt to use a metal complex with an attached chiral ligand as a template was attempted by Lemaire [52]. The Rh complex, ((15,25)-V,V -dimethyl-l,2-diphenylethane diamine)-[Rh(CgHj2)Cl]2 coordinated with optically pure l-(5)-phenylethoxide or phenylethoxide (Rh 1-phenylethanolate) (template) was polymerized in the presence of isocyanate, and the polyurea-supported Rh complex is reacted with isopropanol to extract the template from the polymer backbone. They reported the influence of molecular imprinting on catalytic performance (conversion and enantiomeric excess) for the asymmetric transfer hydrogenation (Table 22.2). The imprinted polymer exhibited higher enantioselectivity compared to a nonimprinted... 

The results of the preparation of polyureas under mild conditions (a pressure of less than 40 atm of carbon dioxide and a temperature around 40 °C) and of poly thioureas (using diphenyl phosphite in pyridine) are compiled in Table 1728). Although the preparation of polyureas from carbon dioxide under drastic conditions (high temperatures and high pressures) or from carbon oxysulfide has been reported, neither preparative method is operative under moderate conditions, nor have the methods for the synthesis of polythioureas from carbon disulfide been described. 

Synthesis and Modification. A series of polyurethanes and polyurethane-ureas of varying degress of hydrophilicity and hydrophobicity and mechanical property were synthesized. The polymers were prepared by a solution polymerization method and consisted of three components a polyether, a diisocyanate, and a chain extender. In our studies, polyurethanes (Table I) were based on a carbowax (polyoxyethylene glycol), MDI (methylene bis-4-phenyl isocyanate) and 1,5-pentanediol. Polyurethane-ureas (Table II) were obtained by substituting the chain extender from a diol to a diamine. The polyurethane-ureas (Table II) were obtained by changing the chain extender from a diol to a more reactive diamine. The polyurea-urethanes (Table III) were obtained by using a diamine terminated polyether instead of the carbowax. 

We recently reported the synthesis of transition metal containing polyamides and polyureas [9], utilizing low temperature interfacial and solution techniques. We have now attempted to extend the solution method to the synthesis of boron containing polymers, viz. [lO]. These polymers are of increasing interest as potential precursors for B-N-C type ceramic materials [10], particularly in fiber form. 

The formation of polyurethane nanoparticles from inverse nano-emulsions (W/O) has also been achieved. Interfacial polyaddition in inverse nano-emulsion is of special interest since this allows the encapsulation of hydrophilic active materials such as proteins or nucleic acids. Thus, taking advantage of the high reactivity of tolylene 2,4-diisocyanate with water molecules, polyurea lipid nanocapsules with aqueous cores obtained from W/O nano-emulsions and prepared by PIT method were designed. Polymer synthesis occurs by in situ interfacial polymerization after nano-emulsion formation. Volatile oils employed as the continuous phase were removed by evaporation and the nanocapsules were redispersed in water. These nanocapsules could be potentially used for encapsulation of both hydrophilic and lipophilic molecules simultaneously. 

When the arenediamines 2,4,6-trimethylbenzene-l,3-diamine and 2,2, 6,6 -tetramethyl-4,4 -methylenediphenylamine were treated under the same reaction conditions with 1.4 equivalents of B0C2O and 1.0 equivalent of DMAP per amino group in acetonitrile at room temperature Method A, work-up with sulfuric acid), 2,4,6-tnmethylbenzene-l,3-diisocyanate 339 and 2,2, 6,6 -tetramethyl-4,4 -meth-ylenediphenyl isocyanate 340 were obtained in yields of 84% and 93%, respectively. Arenediyl diisocyanates play a very important role as monomers for the industrial synthesis of polyurethanes and polyureas [226]. 

Interfacial polymerization techniques can be used to prepare robust microcapsules (about 4 pm) that have selectively incorporated functionality such as catalytic groups in their liquid-core domains. The synthesis of these particles is achieved via an oil-in-oil emulsion in combination with interfacial polymerization methods and allows for the encapsulation of substrates not compatible with water-in-oil or oil-in-water emulsion systems (Kobalija and McQuade, 2006). Often these capsules have polyurea shells that can be formed from w/o emulsions containing reactive polyols and isocyanates. This has been very elegantly demonstrated by McQuade and coworkers for the DMAP-catalyzed acylation transformation of an alcohol within the protected environment of polyurea microcapsules formed from reaction of a polyisocyanate and a poly(vinyl alcohol) in the presence of an amine catalyst (Price et ah, 2006 Poe et al, 2007). 

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