By the reaction of a mixture of isomers (2.4-2.6) of toluene diisocyanate with aliphatic, individual or oligomeric diols (such as polyoxypropylene glycols of different molecular weight) in cyclohexanone, oligodiurethane diisocyanates with the diol component of different nature and length in their structure are synthesized in the first stage. In the second stage, the synthesized oligodiurethane diisocyanates were blocked by monofunctional aliphatic alcohols of normal structure with different lengths of fatty radical. The structure of the latter is confirmed by the absence of absorption bands characteristic of free –NCO groups in the IR spectra. Both series of isolated oligodiureta diisocyanates and oligotetraurethanes are characterized by refractive index and Ubellode drop temperature, molecular weights, content of free –NCO groups, and IR spectra. They are well soluble in esters, ethers, chlorinated and aromatic hydrocarbons, ketones, and aprotic solvents; they are poorly soluble in aliphatic hydrocarbons. The presence in the structure of such compounds of polar urethane groups simultaneously with relatively high molecular weight suggests that they will be useful not only as plasticizers, but also as modifiers of the properties of polymers and composite materials.

The paper describes the synthesis, the reaction of a mixture of isomers (2,4–2,6) of toluilendiisocyanate with a double molar excess of aliphatic individual or oligomeric diols, a number of previously unknown oligodiuretanediols and their physicochemical constants. It is shown that with an increase in the synthesis temperature from 50 to 70 °C, the reaction time to complete depletion in the mixture of free NCO-groups decreases from 8–9 hours to 3–4 hours. The reaction temperature of 70–2 °С should be considered optimal, because at higher temperatures side reactions of free NCO-groups with already formed urethane ones are possible. Because the presence of even a small amount of moisture in the diols can provoke side effects during the urethane formation reaction, all of the above diols were dried from the adsorbed moisture by azeotropic distillation with toluene before use in the reaction. Since the final products are even at the synthesis temperature (68–70 °C) viscous liquids, and there are difficulties with the homogenization of the reaction mass during synthesis, and when unloading the finished product from the reaction plant, in all cases, the synthesis was performed in solution cyclohexanone by 50 % by weight of the final product. Control of the reaction was performed by changing the % wt. free NCO-groups in time. The reaction was considered complete if the measured % wt. free NCO-groups in the reaction mixture for at least one hour twice showed zero. The isolated oligodiuretanediols range from solid at room temperature to very viscous products, which significantly depends on the molecular weight of the diol used in the reaction (ie the concentration of urethane groups formed). They are homogeneous, transparent compounds that are readily soluble in esters, ethers, aromatic and halide-containing, aprotic solvents, ketones, poorly or completely insoluble in aliphatic saturated hydrocarbons. The structure of the synthesized oligomeric products is confirmed by functional analysis, IR–spectra. In the IR-spectra of each of the synthesized oligodiuretanediols there are no absorption bands in the region of 2270 cm-1, which confirms the complete completion of the reaction of urethane formation according to the scheme. At the same time, the absorption bands in the region of 3450 cm-1, 1720 cm-1, 1540 cm-1 are fixed, which are characteristic of the presence of urethane groups in the structure of the target products. As the chain length of the diol component –R– increases in the target product (which synchronously leads to an increase in molecular weight), the intensity of these absorption bands decreases, which is associated with a decrease in the concentration of formed urethane groups in the structure of oligodiuretanediols. The refractive index also decreases synchronously. Synthesized series of oligodiuretanediols can be used for synthesis on its basis of other classes of oligomers with the simultaneous presence in the structure of urethane groups. The ability of such compounds to be soluble in solvents of different nature has been studied, which provides information for the directions of their further use (varnishes, enamels, primers).