Study On Preparation And Properties Of Vegetable Oils-based Non-isocyanate Polyurethane

In this paper,vegetable oil-based cyclic carbonate was prepared by the thiol-ene click chemistry reaction of vegetable oil and its derivatives as starting materials with cyclic carbonate contains thiol group?DMMP?.Vegetable oil-based cyclic carbonate were cured with four diamines with different structure:ethylenediamine?EDA?,1,6-hexanediamine?HDA?,isophoronediamine?IPDA?and m-xylylenediamine?XDA?to produce vegetable oil-based non-isocyanate polyurethane?NIPU?,respectively.Then the effect of structures diamines structures on vegetable oil-based NIPU performance was discussed.The main contents and conclusions as follow:1.DMMP synthesisGlycerol cyclic carbonate was synthesized using glycerol and dimethyl carbonate as raw material,then it reacted with 3-mercaptopropionic acid by esterification reaction to get DMMP.The influence factors in DMMP synthesis process was discussed and the optimum reaction condition was selected.The structure of DMMP was characterized by NMR and FT-IR.2.Study on Preparation and properties of 10-undecenoic acid-based NIPUUndecylenic acid-based bis-cyclic carbonate?UACC?was synthesized via thiol-ene click reaction of 1,4-Butanediol bis?10-undecenoic acid??UABD?containing double bonds and DMMP,then UACC cured with diamines to produce10-undecenoic acid-based NIPU.The influence factors in UACC synthesis process was discussed and the optimum reaction condition was selected.The structure of UACC was characterized by NMR and FT-IR.The structure and properties of10-undecenoic acid-based NIPUs were characterized by NMR,FT-IR,GPC and DSC.The results show that the ratio between secondary and primary alcohols of10-undecenoic acid-based NIPU formation was 1.42:1¹.92:1;Mn of NIPUs was28901³0627 g/mol;Tg of NIPUs showed-16.4¹6.9,and diamines with a ring structure cure afforded higher Tg.3.Study on Preparation and properties of canola oil-based NIPUCanola oil-based Cyclic carbonate?CCAO?was synthesized via thiol-ene click reaction of canola oil as raw material and DMMP,then CCAO was cured with diamines to produce canola oil-based NIPU.The influence factors in CCAO synthesis process was discussed and the optimum reaction condition was selected.The structure of CCAO was characterized by NMR,FT-IR and GPC.The structure and properties of canola oil-based NIPUs were characterized by DMA,TGA and solvent swelling.The results show that NIPU cured with aliphatic diamines had lower Tg and Y-Modulus,and with the increasing segment of diamines,Tg and Young's Modulus decreased.NIPUs cured with IPDA and XDA showed higher Tg and Young's Modulus when the ring was incorporated.NIPU cured with IPDA exhibited highest Tg?41.66??,Young's Modulus?1118 MPa?,Tensile Strength?0.63 MPa?and Elongation at break?159.9%?.Canola oil-based NIPUs cured with HDA,IPDA and XDA exhibited batter thermal stability,the initial decomposition temperature showed more than 253?,T_max more than 390?.NIPU had higher water absorption when the EDA as curing agent.NIPUs had lower toluene swelling when the aliphatic diamines as curing agent.4.Study on Preparation and properties of castor oil-based NIPUCastor oil-based cyclic carbonate was synthesized via thiol-ene click reaction of Undecylenic acid-modified castor oil-based polyene that was synthesized in laboratory and DMMP,and castor oil-based cyclic carbonate were cured with diamines to produce castor oil-based NIPU.The influence factors in castor-based monomer synthesis process was discussed and the optimum reaction conditions was selected.The structure of castor oil-based cyclic carbonate was characterized by NMR,FT-IR and GPC.The structure and properties of castor oil-based NIPUs were characterized by DMA and solvent swelling.The results show that NIPUs cured with aliphatic diamines had lower Tg,Tg and Young's Modulus decreased with the increasing length of diamines segment;Tg increased and Y-Modulus decreased with the degree of crosslinking increased.Tg increased when the ring was incorporated into NIPUs,and IPDA cure afforded highest Tg,showed 29 and 27.5?respectively.Tg showed few influence with the degree of crosslinking increased,but Young's Modulus of XDA cure increased.The water absorption and toluene swelling decreased with the the degree of crosslinking increased.NIPU cured with EDA showed higher water absorption and lower toluene swelling.