Synthesis of a Fully Biobased Polyfunctional Vinyl Oligomer and Their UV Cured Films Prepared via Thiol-ene Coupling

In this paper,a fully bio-based vinyl oligomer with high functionalities was successfully prepared from rapeseed oil by three modification steps:epoxidation of rapeseed oil,solvent-free and catalyst-free ring opening by 10-undecylenic acid followed by esterification with 10-undecenoyl chloride.Then,the renewable polymers were prepared by photo-polymerization of these modified vegetable oils with typical thiol monomers:pentaerythritol tetrakis(3-mercaptopropionate),pentaerythritol tris(3-mercaptopropionate)and 1,2-ethanedithiol.The synthesis of the vinyl oligomer was monitored by nuclear magnetic resonance and Fourier-transform infrared spectroscopy.The average number of the carbon-carbon double bonds of the resulting vinyl oligomer is high to be 7.2.The kinetic of thiol-ene photo-polymerization of vegetable oil-based vinyl oligomer was studied by FTIR-ATR analyses.In addition,the thermo-physical properties,thermal stability and solvent resistance of these UV cured films were characterized.The polymers from 1,2-ethanedithiol exhibit higher gel content,storage modulus and glass transition temperature than those from other thiol monomers due to the high crosslinking densities of the resulting polymers.All polymers show excellent thermal stability up to 290oC.The resulting polymers exhibit thermo-physical properties,excellent water resistance and thermals stability,which is promising to find application in coatings and adhesives.

High Performance Bio-based Polyurethane Elastomers： Effect of Different Soft and Hard Segments

In this work, a series of high performance bio-based polyurethanes（bio-PUs） were synthesized from polylactide（PLA）-based diols, different diisocyanates（TDI, MDI, HDI, IPDI） and chain extender 1,4-butanediol, in which different soft and hard segments are used to adjust their transition temperatures and mechanical properties. Poly（lactide-co-caprolactone）copolymer diols（co-PLAols） instead of PLA diols as the soft segment improved the thermal stability and mechanical properties of the synthesized bio-PUs. Among them, MDI-based bio-PUs have the highest T_g（43.8 °C）, tensile strength（23.5 MPa） and modulus（380.8 MPa）, while HDI-based bio-PUs have the lowest T_g（21.4 °C） and highest elongation at break（580%）. Especially, the bio-PUs synthesized from co-PLAols and MDI demonstrate better mechanical properties,closed to petroleum-based commodities. Furthermore, the obtained bio-PUs display good shape memory properties at body temperature and cytocompatibility. Therefore, these bio-PUs are promising for applications in biomedical fields.