CAJ | 학술논문

为揭示热解过程中木质素中α-O-4连接键的解聚机理，运用密度泛函理论模拟了α-O-4型木质素二聚体模化物苯酚基甘油-α-苯基醚在773 K、101 kPa条件下的热解行为。通过对各步反应热力学焓变的计算，明确了二聚体的初次裂解是Cα—O键和Cα—Cβ键的断裂。根据热力学可能性，将二聚体的后续裂解设计成不同的路径，热解的最终产物有小分子化合物（甲醇、乙醇、乙二醇和环氧乙烷）、苯酚及其对位取代物（对甲基苯酚、对乙基苯酚和对羟基苯甲醇）、苯及其取代物（苯甲醇），酚类产物中较优先的是对甲基苯酚、对乙基苯酚，其次是苯酚。此外，还将α-O4-型二聚体的热解行为与β-O-4型二聚体进行了比较，发现其不同均源于两者结构的差异。
위게시열해과정중목질소중α-O-4련접건적해취궤리，운용밀도범함이론모의료α-O-4형목질소이취체모화물분분기감유-α-분기미재773 K、101 kPa조건하적열해행위。통과대각보반응열역학함변적계산，명학료이취체적초차렬해시Cα—O건화Cα—Cβ건적단렬。근거열역학가능성，장이취체적후속렬해설계성불동적로경，열해적최종산물유소분자화합물（갑순、을순、을이순화배양을완）、분분급기대위취대물（대갑기분분、대을기분분화대간기분갑순）、분급기취대물（분갑순），분류산물중교우선적시대갑기분분、대을기분분，기차시분분。차외，환장α-O4-형이취체적열해행위여β-O-4형이취체진행료비교，발현기불동균원우량자결구적차이。
In order to reveal the depolymerization mechanism of α-O-4 linkages in lignin during the process of py-rolysis, phenolglycerol-α-phenyl ether is selected as the α-O-4 lignin dimer mold compound , and its pyrolysis be-haviors at 773 K and 101 kPa are simulated according to the density functional theory (DFT).Then, the enthalpy changes of each step are calculated .It is found that the dimer pyrolysis starts from the dissociations of C α—O and Cα—Cβbonds.According to the thermodynamics possibility , the following pyrolysis is designed into different paths, and the final pyrolytic products are found to contain small molecule compounds (methanol, ethanol, ethy-lene glycol and ethylene oxide ) , phenol and para-substituted phenols ( p-methyl phenol , p-ethyl phenol and p-hydroxybenzyl alcohol ) , benzene and substituted benzene ( benzyl alcohol ) .In all these phenolic compounds , p-methyl phenol and p-ethyl phenol are the most possible products , which are followed by phenol .In addition , the pyrolysis behaviors of α-O-4 and β-O-4 lignin dimers are compared .The results show that all the differences be-tween the two lignin dimers are attributed to their different structures .