Non-isocyanate polyurethane/epoxy hybrid materials with different and controlled architectures prepared from a CO₂-sourced monomer and epoxy via an environmentally-friendly route

Abstract

Polyurethane/epoxy hybrid materials from CO 2 -sourced monomer were prepared via an environmentallyfriendly and non-toxic route, which avioded the use of toxic isocyanate. A series of non-isocyanate polyurethane (NIPU)/epoxy hybrid materials, with different and controlled architectures, were synthesized from CO 2 , polypropylene glycol diglycidyl ether (PPGDGE), amines and diglycidyl ether of bisphenol-A (BADGE). Around 12 wt% CO 2 was incorporated into PPGDGE to form a five-membered cyclic carbonate (5CC-PPGDGE). The complete conversion and selectivity of PPGDGE were obtained.The kinetics of 5CC-PPGDGE was investigated by reacting it with 1,2-ethylenediamine (EDA) at different temperatures. NH 2 -terminated pre-polymers were obtained by reacting 5CC-PPGDGE with various excessive amines. Finally, the hybrid materials were obtained by curing pre-polymers with BADGE. The results showed that a high content of amine with more functional groups led to better mechanical performances than diamine-based hybrid materials. This is the first time that architectures have been controlled by altering the amine ratio and functionality. And these hybrid materials exhibited satisfactory mechanical performances. The DETA-based and TETA-based materials with high amine ratio exhibited a tensile strength of 15.0 MPa and 12.5 MPa, accompanied with elongation at break of 151.3% and 170.9%, respectively. The gel content, glass transition temperature and thermodynamic stability went up first and then declined with the increase of amine ratio, which demonstrated the architectures of hybrid materials ranged from defective to cross-linked and linear structures.

Synthesis and Characterization of Dimmer-Acid-Based Nonisocyanate Polyurethane and Epoxy Resin Composite

“…Interestingly, comparing the different diamines, the quality order of thermal stability was as follows: TETA > DETA > TEPA. This result was due to a better reactivity between the appropriate structures of TETA and cyclic carbonate [ 27 ]. HNIPU-3451 had the highest Td 5% , about 62 °C increase in comparison with NIPU-34, which illustrates that epoxy resin and high reactive amine can obviously improve the thermal stability.…”

Isocyanate-Free Fully Biobased Star Polyester-Urethanes: Synthesis and Thermal Properties

“…[14,15] On the other hand, amine-terminated PHU prepolymers are first synthesized with an amine excess and are then cross-linked by reacting with polyfunctional epoxy monomers in a second step. [16][17][18] Similarly, amine-terminated PHU have been cross-linked with other functional groups such as acrylic or methacrylic monomers. [19,20] Hybrid siloxane-polyhydroxyurethanes thermosets have been obtained from siloxane-based cyclic carbonate monomers.…”

Preparation of five‐membered bis(cyclic carbonate)s at atmospheric pressure for polyhydroxyurethane coatings

“…[4][5][6][7] Since the NCO group is not required in the two-component raw materials, cyclic carbonates are environmentally friendly. [10][11][12] Among all the cyclic carbonates, fivemembered bis(cyclic carbonate)s have stable performance and are the most widely studied. 8,9 Such structures can lead to hydrogen bonding, and thus they have better thermal and mechanical properties.…”