西茜,史雅枚,安华良,赵新强,王延吉

• 1:河北工业大学化工学院河北省绿色化工与高效节能重点实验室化工节能过程集成与资源利用国家地方联合实验室

摘要(Abstract)：

乙酰丙酸(LA)羟醛自缩合是制备液体生物燃料过程中重要的碳链增长反应。为克服液体酸存在的腐蚀和环境污染等缺点,弥补固体酸存在的活性温度较高和选择性较低等不足,以酸性离子液体[HS03-b-mim]CF3S03为催化剂,催化LA自缩合反应。利用液相色谱-质谱技术确定了主要产物(C9～C15),并建立了LA自缩合反应网络。结果表明,分子量为214的C10产物具有2种结构:直链结构的(Z)-3-乙酰基-4-甲基-3-庚烯二酸和(E)-4-甲基-6-氧代-4-壬烯二酸,以及环状结构的3-(2-甲基-5-氧代-2-四氢呋喃基)-4-氧代戊酸和5-(2-甲基-5-氧代-2-四氢呋喃基)-4-氧代戊酸;分子量为196的C10产物为环状结构的5-((2-甲基-5-氧代-2-四氢呋喃基)甲基)呋喃-2(3H)-酮、5-甲基-4-(2-甲基-5-氧代-2-四氢呋喃基)呋喃-2(3H)-酮和(E)-4-甲基-5-(5-氧代-4,5-二氢-2-呋喃基)-4-戊烯酸。上述结果能够为LA自缩合反应的深入开展奠定基础。

关键词(KeyWords)： 乙酰丙酸;羟醛自缩合反应;酸性离子液体;反应网络

Abstract:

Keywords:

基金项目(Foundation): 河北省基础研究计划自然科学基金和重点基础研究项目(18964308D)

作者(Author): 西茜,史雅枚,安华良,赵新强,王延吉

参考文献(References)：

• [1]LI Z,ZHANG J J.Efficient C-C bond formation between two levulinic acid molecules to produce C10 compounds with the cooperation effect of Lewis and Br?nsted acids[J].ACS Sustainable Chemistry&Engineering,2018,6(5):5708-5711.
• [2]JING J,ZHANG Y,TANG X.Synthesis of a highly efficient phosphorus-containing flame retardant utilizing plant-derived diphenolic acids and its application in polylactic acid[J].RSC Advances,2016,6(54):49019-49027.
• [3]ZHAO L L,AN H L,ZHAO X Q,et al.TiO2-catalyzed n-valeraldehyde self-condensation reaction mechanism and kinetics[J].ACSCatalysis,2017,7(7):4451-4461.
• [4]徐秀秀,吕喜蕾,傅杰,等.高温液态水中稀硫酸催化糠醛渣降解制备乙酰丙酸[J].高校化学工程学报,2015,29(6):1377-1382.XU X X,LüX L,FU J,et al.Catalytic decomposition of furfural residue with dilute sulfuric acid to produce levulinic acid in high temperature liquid water[J].Journal of Chemical Engineering of Chinese Universities,2015,29(6):1377-1382.
• [5]STOSIC D,HOSOGLU F,BENNICI S,et al.Methanol and ethanol reactivity in the presence of hydrotalcites with Mg/Al ratios varying from 2 to 7[J].Catalysis Communications,2017,89(1):14-18.
• [6]苗双,安华良,赵新强,等.Cu-Mg-Al催化剂制备及催化正丁醛一步合成2-乙基己醇性能研究[J].高校化学工程学报,2019,33(4):832-842.MIAO S,AN H L,ZHAO X Q,et al.Preparation of Cu-Mg-Al catalysts and their application in one-step synthesis of 2-ethylhexanol from n-butyraldehyde[J].Journal of Chemical Engineering of Chinese Universities,2019,33(4):832-842.
• [7]XIN J Y,ZHANG S J,YAN D X,et al.Formation of C─C bonds for the production of bio-alkanes under mild conditions[J].Green Chemistry,2014,16(7):3589-3595.
• [8]GAO H,CHEN J Z.Hydrogenation of biomass-derived levulinic acid toγ-valerolactone catalyzed by PNP-Ir pincer complexes:a computational study[J].Journal of Organometallic Chemistry,2015,797(18):165-170.
• [9]FABA L,DIAZ E,ORDONEZ S.Base-catalyzed condensation of levulinic acid:A new biorefinery upgrading approach[J].ChemCatChem,2016,8(8):1490-1494.
• [10]JING J,ZHANG Y,FANG Z P.Diphenolic acid based biphosphate on the properties of polylactic acid:Synthesis,fire behavior and flame retardant mechanism[J].Polymer,2017,108:29-37.
• [11]CUETO J,FABA L,DIAZ E.Performance of basic mixed oxides for aqueous-phase 5-hydroxymethylfurfural-acetone aldol condensation[J].Applied Catalysis B:Environmental,2017,201:221-231.
• [12]ZHANG X L,AN H L,ZHANG H Q,et al.n-Butyraldehyde self-condensation catalyzed by sulfonic acid functionalized ionic liquids[J].Industrial&Engineering Chemistry Research,2014,53(43):16707-16714.
• [13]田金萍.酸性离子液体催化4,4’-二氨基二苯甲烷合成反应研究[D].天津:河北工业大学,2014.TIAN J P.Synthesis of 4,4'-diaminodiphenylmethane catalyzed by acidic ionic liquids[D].Tianjin:Hebei University of Technology,2014.
• [14]龙向东,李泽龙,高广,等.乙酰丙酸催化加氢制备γ-戊内酯的研究进展[J].分子催化,2014,28(4):384-392.LONG X D,LI Z L,GAO G,et al.Progress in the preparation ofγ-valerolactone by catalytic hydrogenation of levulinic acid[J].Journal of Molecular Catalysis(China),2014,28(4):384-392.
• [15]IDRISS H,KIM K S,BARTEAU M A.Carbon-carbon bond formation via aldolization of acetaldehyde on single crystal and polycrystalline TiO2 surfaces[J].Journal of Catalysis,1993,139(1):119-133.
• [16]BLESSING R W,PETRUS L.Process for the dimerisation of levulinic acid,dimers obtainable by such process and esters of such dimers:US,20060135793A1[P].2006-06-22.