离子液体型大分子光产碱剂的合成及其性能研究-应用化学专业论文.docxVIP

转化率随时间变化明显高于空气中，而 MPBGsⅠ-3、Ⅱ-3 在两种氛围中的转化率相差不多，说明MPBGsⅠ-3、Ⅱ-3能有效的减少氧阻聚作用。不同的引发剂对固 化膜性能的影响较大，MPBGsⅠ-3、Ⅱ-3引发树脂体系所得固化膜硬度为2H。 在相同条件下空气氛围中活性大小关系为：Ⅱ-3＞Ⅰ-3＞Ⅱ-2＞Ⅰ-2；N2氛围中其活性大小关系为：Ⅱ-2＞Ⅱ-3＞Ⅰ-3＞Ⅰ-2；5、季铵盐Ⅰ-2、Ⅱ-2、Ⅰ-3、Ⅱ-3经辐射后均能产生碱性物质，并能引发环 氧树脂E-44的热固化，且引发活性与季铵盐的生色团有重要关系，而当其生色团 相同时，虽然MPBGs体系中的叔胺聚合成大分子后碱性有所下降，但每个单元 中含有多个叔胺单元，所以，在相同条件下，其引发效率关系为：Ⅱ-3＞Ⅰ-3＞ Ⅱ-2＞Ⅰ-2；6、光照前预加热及光照后烘烤有助于提高光产碱剂催化环氧树脂E-44的转 化率，最高转化率可达 82.1%。关键词：季铵盐，大分子光产碱剂，自由基引发，光产碱，离子液体AbstractPhotobasegeneratorsasanewinitiator，itcanproducefreeradicalsandaminesunderUVirradiatiton.Inthispaper，twoketoneammoniumorganoboratesandtheirpolymersweresynthesizedby2-(Dimethylamino)ethylmethacrylateandtetrapheny-boronanion.Thestructureofproductsandtheintermediateswerecharacterizedbymeltingpoint、UV-vis.、FT-IR、H1NMR、TGA.Therelationshipbetweenphotophysicsofthesequaternaryammoniumsaltsandstructureswasinvestigated,thephotoactive-tiesofthosesaltswerealsostudied.ThesesaltsweresynthesizedbytwostepsandthestructureofproductswereconfirmedbyUV-vis,FT-IRandH1NMR.Ⅰ-2isacetophenoneammomiumsalt,Ⅱ-2is4-Hydroxyacetophenoneammomiumsalt.Ⅰ-3、Ⅱ-3weretheirpolymers.TheTGAandtheirmeltingpointshowedtheirgoodthermalstability.ThephotophysicsofquaternaryammomiumsaltsshowedthatthewavelengthrangeoftheirUVabsorptionisbetween220nm-350nminacetonitrile．Theλmaxofabsorptiononlydependsonthechromophore．Neitherthetertiaryamineincludingsubstituentsonthenitrogenatomnorthestructureofthecounterionhadmuchinfluenceoneithertheextinctioncoefficientorthewavelengthofmaximumabsorption.The wavelength of maximum absorption ofⅡ-3 is about 310nm, showed the “redshift”withintramolecularhydrogenbonds.Thekineticsofphotolysisofquaternaryammomiumsaltsinacetonitrilewasdetermined．TheresultsshowedthatthephotolysisreactionofPBGsisafirst-orderreaction.ForII-2,thekineticequationofthephotolysisreactionis：Rd∝0.887[I].SolutionsofⅠ-2、Ⅱ-2werepreparedbydissolvingⅠ-2、Ⅱ-2(0.01mmol)inamixtureofDMF(8mL)andH2O(2mL).ThechangesinPHwereobservedasafunctionoftheirradiationtimeuponirradiationwithUVlight.ThePHofⅠ-2incr