【作者】 曹彩红；

【导师】 朱新宝；

【作者基本信息】 南京林业大学 ， 化学工艺， 2007， 硕士

【摘要】 甲基丙烯酸缩水甘油酯(GMA)是一种重要的含环氧基的烯类单体,具有很高的反应活性,广泛应用于涂料、光固化材料、胶粘剂、医药等方面。本论文以六次甲基四胺为催化剂,对羟基苯甲醚为阻聚剂,采用酯化闭环两步法制备出甲基丙烯酸缩水甘油酯(GMA)。在第一步采用六次甲基四胺为环氧基开环催化剂,国内外文献至今尚无报道。通过对第一步环氧基开环催化剂的筛选,发现吡啶、喹啉、1-甲基咪唑、KOH+PEG400、六次甲基四胺等较好,但是由于采用喹啉所得产品的颜色较深,KOH+PEG400所得产品产率较低,最后选定六次甲基四胺作为催化剂。在甲基丙烯酸缩水甘油酯的制备中,研究了反应条件诸如:物料配比、催化剂用量、反应时间、反应温度和阻聚剂用量对甲基丙烯酸缩水甘油酯的环氧值、有机氯及其原料转化率、产物产量的影响和变化规律。研究发现,MAA和ECH的摩尔比在1:1.05—1:1.4的范围内产品质量较好,随着温度和催化剂用量的增加,产物质量特别是环氧值会有所下降,但是产率不断上升,反应温度很低时,环氧值很高,但是产率很低。通过正交设计确定了最佳工艺条件为:开环反应:六次甲基四胺用量0.7%(占反应物总量的质量百分比),阻聚剂用量0.3%(占反应物总量的质量百分比),ECH:MAA的摩尔比为1.3:1,温度80℃,反应时间7h ;闭环反应:氯醇酯: NaOH的摩尔比为1:0.9,反应温度40℃,反应时间5h。GMA产率为80.0%左右,环氧值为0.485eq/100g。单因素研究发现,甲基丙烯酸和环氧氯丙烷的摩尔比小于1:1.4,温度大于90℃,催化剂用量大于0.7%时,反应时间大于7小时,副反应加速,产品质量和产率均会下降,但是催化剂和时间对产品的影响较小。采用红外光谱(IR)和气质联用(GC-MS)对所合成的产品进行了表征,证明所得产品为GMA。更多还原

【Abstract】 Glycidyl methacrylate (GMA) is an important vinyl monomer with epoxy group. It is a high active monomer which is widely used in coating,light-solidfied material ,adhensive ,medicine and so on..Using Hexamethylenetetramine as the catalyst and P-Hydroxyanisole as the inhibitor, glycidyl methacrylate (GMA) were prepared by two-step method successfully. It was not reported on the synthesis of Glycidyl methacrylate in articles till now.Several catalysts used in ring- opening reaction were filtrated systemicly. Quinoline ,1-methyl imidazole,pyridine,KOH+PEG400 and hexamethylenetetramine all had good activity.Hexamethylenetetramine was the better one.The influences of reaction parameters, such as raw material ratio, concentration of catalyst, reaction temperature, reaction time and concentration of inhibitor on the preparation of middle product were studied in 1st reaction, and the influences of reaction temperature , concentration of NaOH solution, reaction time and dosage of NaOH on glycidyl methacrylate(GMA) yields was also investigated in 2st reaction . GMA has been analyzed and characterized. The product qulity is better when the material volume ratio of ECH and MAA ranges from 1:1.05 to1:1.4. Product qulity decreases with the increase of the catalyst concentrations and the temperature of reaction ,but the yield of GMA rise.when the temperature of reaction is too low, The product qulity is better but the yield lower.The optimum reaction conditions are obtained by orthogonal exptl. design; ring-opening reaction:n(MAA):n(ECH) = 1:1.3, Hexamethylenetetramine catalyst 0.7%,reaction temp. is 80℃ , reaction time is 7 h, and concentration of inhibitor is 0.3%. ring-closing reaction : n(middle product):n(NaOH)=1:0.9, reaction temp. is 40℃, reaction time is 5 h. Under these conditions the yield of product can be reached 80.0 %.Study on single factor showed: n(MAA):n(ECH) < 1:1.4 ,concentration of catalyst >0.7%or reaction temperature higher than 90℃accelerated by-product reaction, product quality declined rapidly. Dosage of catalyst and reaction time increased, reaction accelerated, but it was not clear.GMA were investigated by Infrared Spectrum and Gas chromatogram-mass Spectrum.更多还原