四官能度酚合成
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摘要
四酚基乙烷是一种重要的工业产品和原材料，由于其高对称性、刚性强以及荧光性，可以作为特种环氧和氰酸酯的原料，通用型环氧树脂固化剂，酚醛树脂改性剂和光致抗蚀剂，应用于胶黏剂、电子封装材料等。国内少有关于四酚基乙烷及其同系物合成的相关报道。本论文采用苯酚与乙二醛为反应原料，离子交换树脂作为催化剂，研究四酚基乙烷合成反应，建立四酚基乙烷产率测定方法，探索四酚基乙烷合成反应机理，采用2.6-二甲基苯酚、苯酚与乙二醛、戊二醛相互反应合成四酚基乙烷同系物，对四酚基乙烷及其同系物荧光性进行探讨。主要工作如下：
1、在NO.732离子交换树脂催化下，苯酚与乙二醛反应合成四酚基乙烷，利用质谱仪，傅立叶红外光谱仪和核磁共振波溥仪对其结构进行表征；建立四酚基乙烷产率测定方法，讨论反应物配比和反应时间对四酚基乙烷产率的影响。结构表明，苯酚与乙二醛的反应产物为四酚基乙烷。液质联用可以有效测定四酚基乙烷产率，四酚基乙烷产率随反应物配比先增加后下降，随反应时间增加而升高，当反应物配比为15:1，反应时间为32h时四酚基乙烷产率达最高78.8%。
2、研究四酚基乙烷合成反应机理，利用质谱仪，傅立叶红外光谱仪和核磁共振波溥仪监测苯酚与乙二醛的反应产物。结构表明，苯酚与乙二醛反应生成的中间产物上的羟基不稳地，与邻位碳上的氢发生消去反应，生成二酚基乙炔、三酚基乙烯，提出了四酚基乙烷合成机理。
3、在四酚基乙烷合成机理上，以2.6-二甲基苯酚、苯酚与乙二醛、戊二醛相互反应合成四酚基乙烷同系物，采用质谱仪，傅立叶红外光谱仪和核磁共振波溥仪表征产物。结果表明，合成产物为1,1,2,2-（四对羟基2，6二甲基苯基）乙烷、四酚基戊烷和1,1,5,5-（四对羟基2，6二甲基苯基）戊烷。
4、研究四酚基乙烷及其同系物的荧光特性。结果表明，四酚基乙烷拥有荧光特性，荧光光谱中有三个峰，最大发射峰波长为350nm；1,1,2,2-（四对羟基2，6二甲基苯基）乙烷由于甲基取代苯环羟基邻位而产生空间位阻，四酚基戊烷由于长链段的引入破坏了分子共平面性，荧光减弱。
Tetraphenol ethane is useful and important chemical products andstarting materials, owing to its excellent properties such as highsymmetry, strong rigidity and fluorescence properties. It can be rawmaterial of special epoxy resin and cyanate, curing agent of universalepoxy resin, modified agents of phenolic resin and corrosion agent tolight, and it is widely used as adhesive, electronic packaging materials,etc. However, the reaction about tetraphenol ethane and its homolog isseldom reported. In this paper, condensation reaction of phenol andglyoxal has been carried out using isopropyl alcohol as solvent in thepresence of No.732cationic exchange resin as catalyst, an effectivemethodology to analysis and calculate the yield of tetraphenol ethane wasbuilt, the reaction mechanism of tetraphenol ethane was studied, phenol,other three kinds of tetraphenolic compounds were designed andsynthesized by the reaction of glyoxal and2,6-Dimethylphenol, phenoland glutaraldehyde, glutaraldehyde and2,6-Dimethylphenol,fluorescence properties of tetraphenol ethane and its homolog wasdiscussed.
1、Condensation reaction of phenol and glyoxal has been carried out using isopropyl alcohol as solvent in the presence of No.732cationicexchange resin as catalyst. An effective methodology to analysis andcalculate the yield was built under the help of combination of highperformance liquid chromatograph and mass spectrometer. With thismethod, the impacts of different react condition (ratio of phenol andglyoxal, reaction time) on ultimate yield were clarified. The result showsthat when the concentration of phenol is increased, the yield wouldincrease at first, then decreased. The yield will increase with theincreasing of reaction time from0h to32h. The maximum yield is78.8%
2、This paper intend to investigate the reaction of phenol and glyoxalcatalyzed by cationic exchange resin and monitor the structures ofintermediates and final products by ESI-MS, FTIR and NMR. The resultshows that the reaction of phenol and glyoxal producesp-hydroxyphenylacetaldehyde, diphenylacetaldehyde, diphenylacetylene,triphenyl ethylene and tetraphenol ethane.1,2-Diphenyl dihydroxylethane and1,1,2-triphenyl hydroxyl ethane are not found to clarify thehydroxide group produced by the reaction of phenol and glyoxal isunstable and easy to eliminated H2O with H atom. And modified reactionmechanism of phenol and glyoxal was suggested.
3、Other three kinds of tetraphenolic compounds were designed andsynthesized by the reaction of glyoxal and2,6-Dimethylphenol, phenoland glutaraldehyde, glutaraldehyde and2,6-Dimethylphenol based on the reaction mechanism of tetraphenol ethane. The result shows that theproducts the reaction of glyoxal and2,6-Dimethylphenol, phenol andglutaraldehyde, glutaraldehyde and2,6-Dimethylphenol are1,1,2,2–tetrakis (2,6-dimethyl-4-hydroxyphenyl) ethane, tetraphenol pentane and1,1,5,5-tetrakis (2,6-dimethyl-4hydroxyphenyl) pentane.
4、Fluorescence properties of tetraphenol ethane and its homologwas discussed. The result shows that tetraphenol ethane has fluorescenceproperties its fluorescence emission is a series bands at about314nm,334nm and353nm. Fluorescence properties of1,1,2,2–tetrakis (2,6-dimethyl-4-hydroxyphenyl) ethane abate because of methyl replace thehydrogen of benzene ring and produce steric hindrance. Fluorescenceproperties of tetraphenol pentane abate because of introduction of longchain which destroys the coplanarity of tetraphenol ethane.
1、在NO.732离子交换树脂催化下，苯酚与乙二醛反应合成四酚基乙烷，利用质谱仪，傅立叶红外光谱仪和核磁共振波溥仪对其结构进行表征；建立四酚基乙烷产率测定方法，讨论反应物配比和反应时间对四酚基乙烷产率的影响。结构表明，苯酚与乙二醛的反应产物为四酚基乙烷。液质联用可以有效测定四酚基乙烷产率，四酚基乙烷产率随反应物配比先增加后下降，随反应时间增加而升高，当反应物配比为15:1，反应时间为32h时四酚基乙烷产率达最高78.8%。
2、研究四酚基乙烷合成反应机理，利用质谱仪，傅立叶红外光谱仪和核磁共振波溥仪监测苯酚与乙二醛的反应产物。结构表明，苯酚与乙二醛反应生成的中间产物上的羟基不稳地，与邻位碳上的氢发生消去反应，生成二酚基乙炔、三酚基乙烯，提出了四酚基乙烷合成机理。
3、在四酚基乙烷合成机理上，以2.6-二甲基苯酚、苯酚与乙二醛、戊二醛相互反应合成四酚基乙烷同系物，采用质谱仪，傅立叶红外光谱仪和核磁共振波溥仪表征产物。结果表明，合成产物为1,1,2,2-（四对羟基2，6二甲基苯基）乙烷、四酚基戊烷和1,1,5,5-（四对羟基2，6二甲基苯基）戊烷。
4、研究四酚基乙烷及其同系物的荧光特性。结果表明，四酚基乙烷拥有荧光特性，荧光光谱中有三个峰，最大发射峰波长为350nm；1,1,2,2-（四对羟基2，6二甲基苯基）乙烷由于甲基取代苯环羟基邻位而产生空间位阻，四酚基戊烷由于长链段的引入破坏了分子共平面性，荧光减弱。
Tetraphenol ethane is useful and important chemical products andstarting materials, owing to its excellent properties such as highsymmetry, strong rigidity and fluorescence properties. It can be rawmaterial of special epoxy resin and cyanate, curing agent of universalepoxy resin, modified agents of phenolic resin and corrosion agent tolight, and it is widely used as adhesive, electronic packaging materials,etc. However, the reaction about tetraphenol ethane and its homolog isseldom reported. In this paper, condensation reaction of phenol andglyoxal has been carried out using isopropyl alcohol as solvent in thepresence of No.732cationic exchange resin as catalyst, an effectivemethodology to analysis and calculate the yield of tetraphenol ethane wasbuilt, the reaction mechanism of tetraphenol ethane was studied, phenol,other three kinds of tetraphenolic compounds were designed andsynthesized by the reaction of glyoxal and2,6-Dimethylphenol, phenoland glutaraldehyde, glutaraldehyde and2,6-Dimethylphenol,fluorescence properties of tetraphenol ethane and its homolog wasdiscussed.
1、Condensation reaction of phenol and glyoxal has been carried out using isopropyl alcohol as solvent in the presence of No.732cationicexchange resin as catalyst. An effective methodology to analysis andcalculate the yield was built under the help of combination of highperformance liquid chromatograph and mass spectrometer. With thismethod, the impacts of different react condition (ratio of phenol andglyoxal, reaction time) on ultimate yield were clarified. The result showsthat when the concentration of phenol is increased, the yield wouldincrease at first, then decreased. The yield will increase with theincreasing of reaction time from0h to32h. The maximum yield is78.8%
2、This paper intend to investigate the reaction of phenol and glyoxalcatalyzed by cationic exchange resin and monitor the structures ofintermediates and final products by ESI-MS, FTIR and NMR. The resultshows that the reaction of phenol and glyoxal producesp-hydroxyphenylacetaldehyde, diphenylacetaldehyde, diphenylacetylene,triphenyl ethylene and tetraphenol ethane.1,2-Diphenyl dihydroxylethane and1,1,2-triphenyl hydroxyl ethane are not found to clarify thehydroxide group produced by the reaction of phenol and glyoxal isunstable and easy to eliminated H2O with H atom. And modified reactionmechanism of phenol and glyoxal was suggested.
3、Other three kinds of tetraphenolic compounds were designed andsynthesized by the reaction of glyoxal and2,6-Dimethylphenol, phenoland glutaraldehyde, glutaraldehyde and2,6-Dimethylphenol based on the reaction mechanism of tetraphenol ethane. The result shows that theproducts the reaction of glyoxal and2,6-Dimethylphenol, phenol andglutaraldehyde, glutaraldehyde and2,6-Dimethylphenol are1,1,2,2–tetrakis (2,6-dimethyl-4-hydroxyphenyl) ethane, tetraphenol pentane and1,1,5,5-tetrakis (2,6-dimethyl-4hydroxyphenyl) pentane.
4、Fluorescence properties of tetraphenol ethane and its homologwas discussed. The result shows that tetraphenol ethane has fluorescenceproperties its fluorescence emission is a series bands at about314nm,334nm and353nm. Fluorescence properties of1,1,2,2–tetrakis (2,6-dimethyl-4-hydroxyphenyl) ethane abate because of methyl replace thehydrogen of benzene ring and produce steric hindrance. Fluorescenceproperties of tetraphenol pentane abate because of introduction of longchain which destroys the coplanarity of tetraphenol ethane.
引文
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