Diamines polyaddition

Diamine 108 led to 95% ee for the alkylation of l,3-diphenyl-2-propenyl acetate with 90% yield. By polycondensation with a diacid chloride or polyaddition with a diisocyanate, this ligand led, respectively, to an insoluble poly(amide) 109 or poly(urea) 110 with excellent yields. Poly(amide) 109 gave a better ee (80%) than poly(urea) 110 (38%), albeit with a lower conversion (respectively, 38 and 72%), when they were used as palladium hgands... 

Aromatic polyimides are most useful super engineering plastics which exhibit excellent thermal, electrical, and mechanical properties, and have been used widely in aerospace, electronics, and other industries over the past three decades [ 1 -4]. Aromatic polyimides are generally prepared through a two-step procedure by the ring-opening polyaddition of aromatic diamines to aromatic tet-racarboxylic dianhydrides in NMP (or DMAc) solution giving soluble polyamic acids, followed by thermal cyclodehydration (Eq. 1) [1-5]. 

In addition to the high-pressure polycondensation reactions mentioned above, we have studied the high-pressure polyaddition for the synthesis of high-temperature aromatic polymers such as polyaminoimide from bismaleimide and aromatic diamine, polycyanurates from aromatic dicyanates, and polyiso-cyanurates from aromatic diisocyanates [34,36-40]. 

Linear polymers were obtained by the polyaddition of dicyanates with the compounds, which contain active protons primary and secondary amines, glycols and bisphenols. The reaction with diamines given polyisoureas [30, 31] (Scheme 8). 

The principle of miniemulsion polymerization to polyadditions of epoxyresins was successfully transferred to mixtures of different epoxides with varying diamines, dithiols, or diols which were heated to 60°C to form the respective polymers [125]. The requirement for the formulation of miniemulsions is that both components of the polyaddition reaction show a relatively low water solubility, at least one of them even below 10 5 g l1. The diepoxide bisphenol-A-diglycidylether was successfully used as epoxy component. In order to vary the obtained polymeric structure, tri- and tetra-functionalized epoxides were also used. As amino components a NH2 terminated poly(propylene oxide) with Mw=2032 g mol1, 4,4 -diaminobibenzyl, 1,12-diaminododecane, and 4,4 -di-aminodicyclohexylmethane were applied. As other addition components beside amine, 1,6-hexanedithiol and Bisphenol A were used. The hydrophobic compo-... 

The homopolymerization of carbodiimides affords polyguanidines, which are nylon-1 imides. Because of their thermal instability, the homopolymers have found no utiUty as industrial polymers. Polyguanidines are also obtained in the reaction of hexamethylene-bis(t-butylcarbodiimide) with diamines. The polyaddition reactions of bis-carbodiimides with dialcohols and dithiols also produce the corresponding addition polymers. In the reaction of hexamethylene-bis(t-butylcarbodiimide) the polyaddition reactions proceed across the less sterically hindered C=N bond. Masked bis-carbodiimides, which are thermally unblocked, are also used in crosslinking reactions. 

In139) the researchers studied the nonisothermal kinetics of polyaddition reactions of oxiranes to aromatic amines up to high conversion levels, as well as the kinetic laws governing the curing of epoxide oligomers by diamines under the conditions of a propagating reaction front. 

Tomita, H., Sanda, F., and Endo, T. Structural Analysis of Polyhydroxyurethane Obtained by polyaddition of Bifunctional Five-Membered Cyclic Carbonate and Diamine Based on the Model Reaction, Journal Polymer Sci. A 39 (2001) 851 -859. 

PHD polymer polyols are a special class of filled polyols developed successfully by Bayer, PHD being the abbreviation of the German name polyharnstoff dispersion or polyurea dispersions [67-69]. PHD polyols contain organic urea, oligomeric or polymeric polyurea, finely dispersed in liquid polyether polyols [67-73]. The difference between PHD polyols and graft polyether polyols is the different nature of the solid polymer dispersed (it is a heterocatenary polymer - polyurea - instead of carbocatenary polymer) which is obtained by another synthetic procedure (polyaddition reaction between a diisocyanate and a diamine instead of radical polymerisation). The reaction between the diisocyanate and the diamine, takes place in situ (reaction 6.19), in liquid poly ether. The resultant polyurea being insoluble in polyether, precipitates in the form of very fine particles ... 

Another example of polyaddition-type step-growth polymerization is the preparation of polyurea from the reaction of diisocyanate and diamine, as shown in Equation 2.30. 

Heterochain polymers of the type -(M-X) - contain polar M-X bonds (for reviews see [1,2,12-15]). Such polymers are often prepared by polycondensation of a bifimctional metal halide (M = B, Si, Ge, Sn, Pb, Sb, Ni, Pd, Pt, Ti, Hf) with a bifunctional Lewis base such as a diol, diamine, dihydrazine, dihydrazide, dioxime, diamideoxime, dithiol, diacetylene (Eq. 7-2). Another possibilitiy is the polyaddition of a bifunctional metal hydride to bifunctional alkenes (Eq. 7-3). Mn and mg containing poly(p-xylylenes) of the composition -(-CH2-C6H4-CH2-M-) - were produced by solid-state UV-photopolymerization of a cocondensated mixture of p-xylylene with Mn or mg at 80 K [16]. Prolonged storage of the polymers at ambient temperature under vacuum led to gradual decomposition. 

Step polyaddition (urethane formation) Polyurethanes with large M can be prepared using a method based on the Wnrtz alcohol test. In the presence of a basic catalyst such as a diamine, ionic addition takes place, for example, between 1,4-butanediol and 1,6-hexanediisocyanate ... 

Expoxide EP Bisphenol and epichlorohydine Polyaddition with diamine or diacid None Diamine... 

The poly(ether imide)s derived from ether-containing bis(ether anhydride)s (Scheme 2.8) or polyimides (Scheme 2.9) were prepared via a conventional two-stage procedure involving ring-opening polyaddition of the diamines (Tables... 

Polyaddition and polycondensation reactions usually lead to functional polymers, since the polymers produced are terminated with reactive functional groups. A higher degree of functionality is easily affordable if monomers with additional reactive groups are used that do not participate in the step-growth polymerization. In emulsion polymerizations, neither polyaddition nor polycondensation reactions can be carried out consequently, the miniemulsion technique is of special interest as no diffusion of the monomers takes place. The first polyaddition in miniemulsion were performed in 2000, with the reaction of polyepoxides and hydrophobic diamines, bisphenols, and dimercaptanes [105]. Stable latexes of epoxy resins could be obtained, and apparent molecular weights of up to 20 000 g mol were measured. 

Polyaddition or polycondensation at the droplet/continuous phase interface leads to the formation of nanocapsules. Polystyrene-polyurea core-shell partides were prepared by miniemulsifying the styrene and hydrophobic diisocyanate monomers, followed by the addition of a diamine to the miniemulsion and the radical polymerization of styrene [122]. The presence of a polyurea shell was shown to prevent the migration of an encapsulated dye. Torini et al. carried out the reaction between a diisocyanate dissolved in oil and a diol dissolved in water, added following miniemulsification of the first monomer in the aqueous continuous phase [123]. 

Poly(silamine), (5) which was synthesized through anionic polyaddition reactions between divinylsilanes and diamines in the presence of a lithium catalyst, has unique repeating units,... 

Synthesis of Poly(silamine) Derivatives. As we reported previously, (5) the reaction between dimethyldivinylsilane (DVS) and 3,6-diazaoctane (DAO) in the presence of a lithium catalyst gives the polyadducts [poly(silamine)], the MW of which is controllable from a few hundred to ten thousands (Scheme 1). When piperazine (PIP) was used as a diamine source instead of DAO, the anionic polyaddition reaction proceeds also without any side reaction. (6)... 

On the basis of these results, it is concluded that poly(silamine) derivatives which possess phenylene linkages in the main chain can be obtained by the reaction of VSB with diamine compounds such as DAO and PIP. Fig. 2 summarizes poly(silaniine)s which were synthesized so far by the anionic polyaddition reactions between two kinds of divinylsilanes (DVS and VSB) and two kinds of diamines (DAO and PIP). 

Fig. 2. Poly(silamine) derivatives synthesized by the anionic polyaddition reactions between divinylsilanes (DVS and VSB) and diamines (DAO and PIP)...

In the first stage of our study, three aromatic diamines were used as chain extenders a non-symmetrical chain extender, 2,4-toluene diamine (TDA) two symmetric aromatic diamines 4,4 -methylene dianiline (MDA) and 4,4 -diamino-dibenzyl (DAB). TDA was used in order to improve the mechanical properties and thermal stability. The materials were synthesized by a two steps polyaddition reaction as... 

The principle of miniemulsion polymerization to polyadditions of epoxy-resins was successfully transferred to mixtures of different epoxides with varying diamines, dithiols, or diols heated to 60 °C to form the respective polymers [24]. One requirement to formulate miniemulsions is that both components of the polyaddition reaction have a relatively low water solubility (at least one with solubihty <10-5 g L-i) ... 

Polycondensation is a typical method for polyimide syntheses, which need aromatic tetracarboxylic acids and aromatic diamines as monomers. Figure 10.1 shows that the polymerization process goes through two reactions The ring-opening polyaddition of aromatic diamines to aromatic tetracarboxylic dianhydrides in solution at room temperature gives soluble precursor polyamic acids, followed by solid-state thermal cyclodehydration to polyimides. 

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