【作者】 姜勇；

【导师】 魏俊富；

【作者基本信息】 天津工业大学 ， 应用化学， 2004， 硕士

【摘要】 制备了三种Zr：Ti分别为1：2、1：3、1：4的TiO₂-ZrO₂／SO₄^2-型固体超强酸。测得其Hammett酸度值均小于-14.52。以这三种固体超强酸为催化剂，二乙二醇丁醚与多聚甲醛缩合生成二乙二醇丁醚缩甲醛为探针反应，设计正交实验，得到最佳反应条件：催化剂用量5％，反应时间3h，催化剂种类C2（Zr：Ti=1：4）。通过IR、NMR谱图确定了二乙二醇丁醚缩甲醛结构为：C₄H₉OCH₂CH₂OCH₂CH₂OCH₂OCH₂CH₂OCH₂CH₂OC₄H₉。 采用最佳工艺条件合成了O-9、O-15、O-20缩甲醛三种分子量较大的缩醛型聚醚，产率分别为88.6％、81.9％、75％。同原料聚醚相比，缩醛型聚醚浊点降低，表面张力、黏度增大，泡沫性和乳化性变好。随着分子中EO数的增加，缩醛型聚醚的浊点提高，泡沫高度增加，黏度增大，表面张力增加，乳化性降低。与分子量相近的聚醚表面活性剂相比，缩醛型聚醚具有较低的表面张力，低泡性和更优良的乳化性。 研究了三种缩醛型聚醚的水解性能：O-9缩甲醛经乳化剂乳化后的水解速度比不乳化直接水解时快近20倍，而O-15缩甲醛和O-20缩甲醛经乳化剂乳化后水解速度只提高1.4到2.38倍。再选用性能更好的乳化剂（O-9），三者速度均可再提高1.14到1.31倍。pH值一定时，随着温度的增加，缩醛的水解速率总体上是加快的。pH值较高时，水解速率在高温段变化明显，pH值较低时，水解速率在低温段变化明显。温度一定时，随着pH值减小，水解速率增加。三种缩醛型聚醚随着EO数的增加，水解速度加快。确定了缩醛型聚醚的水解反应为一级动力学反应，得出了水解速率、半衰期、活化能等动力学参数。 比较了O-9缩甲醛、O-20缩甲醛、水解后的O-20缩甲醛生物降解情况：降解后三个体系中的pH值均有所下降，未经水解的体系pH值由7下降到5.5，水解体系的pH值由9下降到6.5。考察O-20缩甲醛水解体系和未水解体系的浊度变化，前者的浊度明显大于后者。降解速率为：水解后的O-20缩甲醛降解最快，未经水解的O-20缩甲醛的降解速率次之，O-9缩甲醛降解最慢。确立了降解反应为一级动力学反应，推出了动力学方程。更多还原

【Abstract】 three TiO2-ZrO2/SO42- type solid superacids were prepared with the ratio of Zr to Ti was 1:3,1:4,1:5 respectively .Their acidity were all less than -14.52 by Hammett method and the structure was determined by IR. Acetals were prepared by condensation of diethyleneglycol monobutyl ether with paraformaldehyde in the presence of the above catalysts. The optimum condition obtained was: the amount of catalyst 5%, reaction time 3h, catalyst type Zr:Ti=1 :4 and the yield was high to 83.9%. The effect of the different factors on the acetalation was discussed and the structureof the acetal was C4H9OCH2CH2OCH2CH2OCH2OCH2CH2OCH2CH2OC4H9 determined by IR,NMR.Three noncyclic acetal-linked cleavable surfactants were prepared based on the optimum condition by condensation of para formaldehyde with polyethers O-9, O-15, O-20. The yield was 88.6%, 81%, 75%, respectively and the structure was determined by NMR. Comparing with polyethers which were raw materials, the acetals’ cloud points were decreased, surface tensions raised, foam heights were low and the emulsifications were improved. Comparing with polyether which had the similar molecular, except cloud point and viscosity ,the other properties of the acetal-linked cleavable surfactant were all improved : the surface tension was decreased from 40.1 mN·m-1 to 36.5 mN·m-1, the emulsification was improved from 153s to350s, the original foam height was reduced from 60mm to 35mm.The study of hydrolysis of acetals indicated that the hydrolytic rate constant of acetals of O-9(was abbreviated for O-9s) was increased nearly 20 times after emulsified and those of theO-15s and O-20s were only improved 1.4 to 2.38 times. All of them can ascend 1.14 to 1.38 times further. When the pH value was invariable, the hydrolytic rate was accelerated as the temperature raised. The change range of hydrolytic rate was larger in high temperature when pH was high and was opposite when pH was low. When the temperature was fixed, the hydrolytic rate was fasterwith the lower of pH value. The more the molecular of acetal was, the more sensitive the hydrolysis to pH was. The low active energy can make hydrolysis fast. Hydrolytic Kinetics was studied and the result was: the hydrolytic formula was first class and the hydrolytic rate constant, half life, active energy were all obtained.The pH value of O-9s, O-20s and O-20s’(after hydrolysis) were decreased from 7 to 5.5 and from 9 to 6.5,respectively. The turbidity of O-20s’ was more obviously than that of O-20s and the rate of biodegradation rate of O-20s’ was the fastest, the O-20s was the second and the O-9s was the third. The biodegradation kinetics formula was the first class and accorded with the experimental data.更多还原