A series of eight aliphatic polycarbonate (PC) glycols with various methylene numbers (HO−[(CH2) m OC(O)O] n −(CH2) m −OH, m = 3, 4, 5, 6, 7, 8, 9, and 10) were employed as a soft segment for a synthesis of polyurethane elastomers (PUEs). First of all, viscosity, glass transition temperature, melting point, and crystalline structure of these new PC-glycols were investigated. The PC-glycol-based PUEs were synthesized using the PC-glycols, 4,4′-diphenylmethane diisocyanate, and 1,4-butanediol by a one-shot method. Differential scanning calorimetry and small-angle X-ray scattering measurements revealed that the degree of microphase separation of the PC-glycol-based PUEs became first weaker and then stronger with increasing number of methylene groups of PC-glycols. The threshold carbon number for the degree of microphase separation was six. In the tensile testing, Young’s modulus of the PUEs decreased and increased with an increase in the methylene number, which can be explained by the degree of microphase separation. Tensile strength and elongation at break of the PC-glycol-based PUEs increased and decreased with increasing the number of methylene groups. These results are associated with the ease of packing of the PC-glycol chains.

Polyurethane elastomers (PUEs) were prepared with poly(oxytetramethylene) glycol (M n ¼2000), 4,4¢-diphenylmethane diisocyanate, 1,4-butanediol (BD) and 1,1,1-trimethylol propane (TMP) by a prepolymer method. To evaluate the effect of curing temperature and the ratio of curing and crosslinking agents ((BD/TMP)¼(10/0 and 8/2)(wt/wt)) on deformation behavior, four different samples were prepared. In the small-angle X-ray scattering (SAXS) profile for the PUEs prepared at 120 1C, a four-point pattern was observed with the preferred tilt being produced by local torques exerted within the strained soft segments from the initial deformation. At near failure strains, strong meridional scattering appeared and the four-point pattern disappeared. In contrast, the PUEs at 80 1C produced meridional scattering through the deformation. As the microdomain structure of the PUEs prepared at 120 and 80 1C initially possessed cylinder-and sphere-like structures, respectively, the cylinder-like structure might have produced the four-point pattern. Obvious changes in interdomain spacing of PUEs at 120 1C during the deformation process were observed in comparison with the spacing at 80 1C. This was due mainly to the formation of a well-developed, networked, cylinder-like microdomain structure. Strain-induced crystallization of the soft-segment chains evaluated by wide-angle X-ray diffraction results was also consistent with the results from SAXS.

We have demonstrated a hydrolysis reaction of polyurethane (PU) under high pressure of carbon dioxide (CO 2 ) in water. We employed the PU sample, poly(methylene bis-(1,4-phenylene)hexamethylene dicarbamate), denoted as M-PU, which was synthesized from 4,4 0 -diphenyl methane diisocyanate and 1,4-butane diol (BD). The optimum hydrolysis reaction condition was 190 8C under CO 2 pressures over 4.1 MPa in water medium, and 93% hydrolysis of M-PU was achieved. After the reaction, the water-soluble parts were obtained, and isolated by column chromatography. The isolated products were 4,4 0 -methylenedianiline (MDA) and 1,4-butane diol (BD), which were components of repeating unit of M-PU. In addition, the hydrolysis reaction gave no byproduct. This hydrolysis under high pressure of CO 2 with water is a reaction by which M-PU is selectively hydrolyzed into MDA and BD by cleaving urethane linkage. Moreover, the resulting hydrolyzed products were easily obtained by evaporation of aqueous layer after the reaction, indicating an efficient chemical recycling of PU was achieved.

In order to develop a chemical recycling system of polyurethanes (PUs), environment‐friendly hydrolysis of two types of aliphatic PUs was studied under pressured CO2 in water, in which the carbonic acid generated from CO2 acted as an acid catalyst. Two PUs, namely H‐PU or I‐PU, were synthesized starting from 1,4‐butanediol and 1,6‐hexamethylene diisocyanate or isophorone diisocyanate, respectively. The hydrolysis of PUs depended on the experimental conditions, such as the temperature and CO2 pressure. As a result, 98% of H‐PU and 91% of I‐PU were successfully hydrolyzed under the typical conditions of 190 °C for 24 h at 8.0 MPa CO2. The reaction mixtures afforded 1,4‐butanediol and diamines without the formation of any byproducts. Both of these raw materials generated from the originated PUs by selective hydrolytic cleavage of the urethane linkages, and they were easily isolated in high yields simply by evaporation of the water‐soluble components within the reaction mixture. By comparing the results of the two aliphatic PUs with those of an aromatic PU (M‐PU), the hydrolyzability was found to decrease in the order H‐PU, I‐PU, and M‐PU. The difference can be ascribed to the hydrophilicity of the aliphatic or aromatic groups connected to the urethane moieties at the terminals of PUs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45897.

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