Synthesis And Characterization Of Cationic Photocuring Monomer Oxetane

The cationic active monomer oxetane is a high-end variety of reactive diluents.In the curing process,it has the characteristics of not being inhibited by oxygen,small volume shrinkage of ring-opening polymerization,strong adhesion,high hardness,etc,and is especially suitable for high-precision stereolithography and rapid prototyping.In this paper,3-ethyl-3-hydroxymethyloxetane(OXT101),trimethylolethane,dimethyl carbonate and the like were used as starting materials to synthesize a series of monofunctional,difunctional,Hybrid oxetane active monomer with special function and its structure was characterized.The specific research contents and conclusions are as follows:(1)Monomer MOXA was synthesized by condensation and cleavage with trimethylolethane and dimethyl carbonate as raw materials;then MOXB was synthesized by etherification with MOXA and benzyl chloride;OXT101 was used as the starting material to esterify with methanesulfonyl chloride,and then etherified with ethylene glycol to synthesize the monomer OGLE containing a flexible ethylene glycol functional group.Three monofunctional cationic active monomers oxetane MOXA,MOXB,OGLE were obtained,and the structure was determined by infrared spectroscopy and nuclear magnetic resonance spectroscopy,and the content was determined by gas chromatography.Content of three monofunctional oxetane monomers(MOXA,MOXB,OGLE): 97.9%,92.0%,98.2%;yield: 78.0%,87.3%,69.1%.(2)MOXA is first esterified with methylsulfonyl chloride,and then subjected to bimolecular condensation reaction with MOXA in an alkaline environment to obtain monomer MOXC;OXT101 and p-dibenzyl chloride as raw materials to synthesize monomer OXT121;BHE-BPA was synthesized from ethylene carbonate as a raw material,and then reacted with OXT101 to obtain monomer OT512.Three kinds of bifunctional cationic active monomers oxetane MOXC,OXT121 and OT512 were obtained.The structure was determined by infrared spectroscopy and nuclear magnetic resonance spectroscopy,and the content was determined by gas liquid chromatography.The content of three kinds of bifunctional monomers(MOXC,OXT121,OT512): 97.7%,96.1%,93.5%;Yield: 74.8%,97.6%,98.3%.(3)Three kinds of methacrylate-containing oxetane monomers OXE30,MOXD,OGME were obtained by transesterification of OXT101,MOXA and OGLE with methyl methacrylate respectively;The oxetane monomer containing double bond structure AEO was obtained by etherification of OXT101 and 3-bromopropene.The oxetane monomer containing siloxane structure OXT610 was obtained by hydrosilylation of monomer AEO with triethoxysilane.Five kinds of hybrid cationic active monomers oxetane OXE30,MOXD,OGME,AEO and OXT610 were synthesized and their structures were determined by infrared spectroscopy and nuclear magnetic resonance spectroscopy.The content was determined by gas chromatography.Contents of five hybrid monomers(OXE30,MOXD,OGME,AEO,OXT610): 99.0%,96.6%,98.9%,99.7%,98.5%;yield: 88.5%,87.0%,80.0%,90.0 %,80.0%.