A simple non-isocyanate route synthesizing crystallizable aliphatic segmented thermoplastic poly(ether urethane)s (PEIUs) and elastomers with high melting temperature (Tm) and good mechanical properties is described. Three poly(ethylene hexanediurethane) prepolymers (PrePEHDUs) were prepared through the self-transurethane polycondensation of bis(hydroxyethyl) hexanediurethane. Melt polycondensation of PrePEHDUs, poly(ethylene glycol)1500, and bis(hydroxyethyl) isophoronediurethane was conducted at 170°C under a reduced pressure of 399 Pa, and a series of segmented PEIUs containing irregular units were synthesized. The PEIUs were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, 1proton nuclear magnetic resonance, 13carbon nuclear magnetic resonance (C-NMR), 2D 13C–1H heteronuclear single quantum coherence (HSQC) NMR, distortionless enhancement by polarization transfer (DEPT)-135 13C-NMR, differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray diffraction, atomic force microscopy, and tensile tests. The PEIUs exhibited a number-average molecular weight up to 20700 g/mol, Tm up to 141.1°C, initial decomposition temperature at over 243.1°C, and tensile strength up to 49.44 MPa. By tuning the length and amount of crystallizable segments, crystallizable PEIU thermoplastic elastomers were prepared. They exhibited tensile strength up to 20.85 MPa, elongation at break above 125.43%, and resilience above 65.69%.
DelebecqEPascaultJPBoutevinB. On the versatility of urethane/urea bonds: reversibility, blocked isocyanate, and non-isocyanate polyurethane. Chem Rev2013; 113: 80–118.
2.
DattaJLewickiM. Investigation of polyurethane elastomer–steel joints using glass lacquer as an adhesive agent. J Elastom Plast2013; 47: 320–326.
3.
GuanJSongYHLinY. Progress in study of non-isocyanate polyurethane. Ind Eng Chem Res2011; 50: 6517–6527.
4.
OchiaiBEndoT. Carbon dioxide and carbon disulfide as resources for functional polymers. Prog Polym Sci2005; 30: 183–215.
5.
KathalewarMSJoshiPBSabnisAS. Non-isocyanate polyurethanes: from chemistry to applications. RSC Adv2013; 3: 4110–4129.
6.
TamamiBSohnSWilkesGL. Incorporation of carbon dioxide into soybean oil and subsequent preparation and studies of nonisocyanate polyurethane networks. J Appl Polym Sci2004; 92: 883–891.
7.
BrocasALCendejasGDeffieuxA. Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate-free polyurethane networks. J Polym Sci Part A Polym Chem2011; 49: 2677–2684.
8.
DiakoumakosCDKotzevDL. Non-isocyanate-based polyurethanes derived upon the reaction of amines with cyclocarbonate resins. Macromol Symp2004; 216: 37–46.
9.
OchiaiBInoueSEndoT. One-pot non-isocyanate synthesis of polyurethanes from bisepoxide, carbon dioxide, and diamine. J Polym Sci Part A Polym Chem2005; 43: 6613–6618.
10.
AnnunziataLDialloAKFouquayS. α,ω-Di(glycerol carbonate) telechelic polyesters and polyolefins as precursors to polyhydroxyurethanes: an isocyanate-free approach. Green Chem2014; 16: 1947–1956.
11.
BährMBittoAMülhauptR. Cyclic limonene dicarbonate as a new monomer for non-isocyanate oligo- and polyurethanes (NIPU) based upon terpenes. Green Chem2012; 14: 1447–1454.
12.
BährMMülhauptR. Linseed and soybean oil-based polyurethanes prepared via the non-isocyanate route and catalytic carbon dioxide conversion. Green Chem2012; 14: 483–489.
13.
BesseVAuvergneRCarlottiS. Synthesis of isosorbide based polyurethanes: an isocyanate free method. React Funct Polym2013; 73: 588–594.
14.
MaierSLoontjensTScholtensB. Isocyanate-free route to caprolactam-blocked oligomeric isocyanates via carbonylbiscaprolactam- (CBC-) mediated end group conversion. Macromolecules2003; 36: 4727–4734.
15.
MaierSLoontjensTScholtensB. Carbonylbiscaprolactam: a versatile reagent for organic synthesis and isocyanate-free urethane chemistry. Angew Chem Int Ed2003; 42: 5094–5097.
16.
ZimmermannJLoontjensTScholtensBJR. The formation of poly(ester-urea) networks in the absence of isocyanate monomers. Biomaterials2004; 25: 2713–2719.
17.
TangDMulderDJNoordoverBAJ. Well-defined biobased segmented polyureas synthesis via a TBD-catalyzed isocyanate-free route. Macromol Rapid Commun2011; 32: 1379–1385.
18.
DeepaPJayakannanM. Solvent-free and nonisocyanate melt transurethane reaction for aliphatic polyurethanes and mechanistic aspects. J Polym Sci Part A Polym Chem2008; 46: 2445–2458.
19.
DeepaPJayakannanM. Solvent-induced self-organization approach for polymeric architectures of micropores, hexagons and spheres based on polyurethanes prepared via novel melt transurethane methodology. J Polym Sci Part A Polym Chem2007; 45: 2351–2366.
20.
RokickiGPiotrowskaA. A new route to polyurethanes from ethylene carbonate, diamines and diols. Polymer2002; 43: 2927–2935.
21.
OchiaiBUtsunoT. Non-isocyanate synthesis and application of telechelic polyurethanes via polycondensation of diurethanes obtained from ethylene carbonate and diamines. J Polym Sci Part A Polym Chem2013; 51: 525–533.
22.
SharmaBUbaghsLKeulH. Synthesis and characterization of alternating poly(amide urethane)s from ε-caprolactam, amino alcohols, and diphenyl carbonate. Polymer2004; 45: 5427–5440.
23.
SharmaBUbaghsLKeulH. Microstructure and properties of poly(amide urethane)s: comparison of the reactivity of α-hydroxy-ω-O-phenyl urethanes and α-hydroxy-ω-O-hydroxyethyl urethanes. Macromol Chem Phys2004; 205: 1536–1546.
24.
SharmaBUbaghsLKeulH. Synthesis and characterization of alternating poly(amide urethane)s from ∊-caprolactone, diamines and diphenyl carbonate. Macromol Chem Phys2004; 205: 1536–1546.
25.
LiCGLiSQZhaoJB. Synthesis and characterization of aliphatic poly(amide urethane)s having different nylon 6 segments through non-isocyanate route. J Polym Res2014; 21: 498.
26.
LiSQZhaoJBZhangZY. Synthesis and characterization of aliphatic segmented poly(ether amide urethane)s through a non-isocyanate route. RSC Adv2014; 4: 23720–23729.
27.
DengYLiSQZhaoJB. Crystallizable and tough aliphatic thermoplastic poly(ether urethane)s synthesized through a non-isocyanate route. RSC Adv2014; 4: 43406–43414.
28.
DengYLiSQZhaoJB. Aliphatic thermoplastic poly(ether urethane)s having long PEG sequences synthesized through a non-isocyanate route. Chin J Polym Sci2015; 33: 880–889.
29.
LiSQZhaoJBZhangZY. Aliphatic thermoplastic polyurethane-ureas and polyureas synthesized through a non-isocyanate route. RSC Adv2015; 5: 6843–6852.
30.
LiSQZhaoJBZhangZY. Crystallizable and tough aliphatic thermoplastic polyureas synthesized through a non-isocyanate route. Ind Eng Chem Res2016; 55: 1902–1911.
31.
LiSQZhaoJBZhangZY. Synthesis and characterization of aliphatic thermoplastic poly(ether urethane) elastomers through a non-isocyanate route. Polymer2015; 57: 164–172.
32.
LiYLiSQZhaoJB. Synthesis and characterization of crystallizable aliphatic thermoplastic poly(ester urethane) elastomers through a non-isocyanate route. Chin J Polym Sci2016; 34(10): 1220–1233.
KlinedinstDBYilgörEYilgörI. Structure-property behavior of segmented polyurethaneurea copolymers based on an ethylene-butylene soft segment. Polymer2005; 46: 10191–10201.
35.
AnandhanSLeeHS. Influence of organically modified clay mineral on domain structure and properties of segmented thermoplastic polyurethane elastomer. J Elastom Plast2012; 46: 217–232.
36.
ZhangXLXiaoJJZhouHJ. Synthesis and characterization of damping polyurethane derived from poly(neopentyl glycol propoxylated succinic acid). J Polym Res2015; 21: 108.
