【作者】 李小童；

【导师】 张杰；

【作者基本信息】 河南科技大学 ， 高分子化学与物理， 2005， 硕士

【摘要】 以双羟基聚醚多元醇和单双键单羟基聚醚为原料, 研究了醇盐化反应、端烯丙基化反应及端烯丙基聚醚粗品的精制工艺, 特别对烯丙基化动力学和反应机理进行探讨, 求得了反应速率方程, 同时对端烯丙基聚醚的结构和性能进行了表征。初步探讨了端烯丙基聚醚的硅氢化反应。首先研究了聚醚的醇盐化技术, 考察了三种醇盐化试剂甲醇钠、金属钠和氢氧化钾的反应活性,结果表明甲醇钠是最佳的醇盐化试剂。进而确定了反应工艺参数( 反应时间、反应温度)、醇盐化试剂的用量及聚醚分子量对羟基转化率的影响,确定了最佳反应工艺条件。其次对双羟基聚醚的端烯丙基化反应进行研究,讨论了反应时间、反应温度、聚醚分子量、烯丙基化试剂的种类和用量对反应的影响。制得了高封端率的端烯丙基聚醚, 并通过多种手段对其结构和性能进行了表征。进行了动力学研究,获得了反应活化能和各反应温度下的反应速率常数, 同时研究结果表明烯丙基化反应级数为2, 反应机理为SN2 亲核取代反应。以单双键单羟基聚醚为原料, 通过链倍增反应制得了端双键聚醚, 并与烯丙基化反应得到的聚醚进行对比。结果表明, 在本研究的工艺条件下通过链倍增反应制得了端双键聚醚的分子量分布过宽。研究了端烯丙基聚醚粗品的精制工艺, 以改进的中和吸附法对端烯丙基聚醚粗产物进行精制, 考察了中和剂用量和吸附剂用量对过滤速度的影响, 讨论了精制产物酸值和色度的影响因素, 获得了精制过程的最佳工艺参数。更多还原

【Abstract】 The alkoxylation reaction, terminal allylation reaction and the purification technics of crude allyl-terminated polyether were studied as the polyether polyol with double hydroxyl and polyether with one hydroxyl and one unsaturated link were raw material. Especially the kinetic and reaction mechanism of allylation reaction were discussed and the rate equation was drawn. Simultaneously, the structure and performance of the allyl-terminated polyether was characterized and the hydrosilylation reaction of the allyl-terminated polyether was discussed briefly. Firstly the technics of polyether alkoxylation was studied. The activation of three alkoxylation reagents including NaOMe, sodium and KOH was investigated which indicated that NaOMe was the best alkoxylation reagent. The influence of reaction time, reaction temperature, molecular weight of polyether and the dosage of alkoxylation reagent on the alkoxide introduction rate was studied and the optimum condition was determined by experimentation. The terminal allylation reaction was studied which was influenced by reaction time, reaction temperature, category and dosage of allylation reagent and molecular weight of polyether. After allyl-terminated polyether with high introduction rate was prepared, the structure and performace of product was tested and characterized by menas of instruments. The activation energy and rate constant of the allylation reaction was calculated in virtue of kinetic study. The kinetics study indicated that the allylation reaction of polyether was second order and its reaction mechanism was SN2 nucleophilic substitution. The polyether with one hydroxyl and one unsaturated link which was initiated from allyl alcohol also was used to prepare unsaturated link-terminated polyether by doubling chain reaction, but the product was not appropriate for sealants because of its broad molecular weight distribution. The purification of crude allyl-terminated polyether was studied which was carried by modified neutralization-absorption method. The influence of the dosage of neutralization reagent and absorption reagent on the filtration rate, product acid number and color was studied and the optimum purification technique was drawn. The slyl-terminated polyether was prepared from allyl-terminated polyether and DMS by way of hydrosilylation reaction. As the catalyst of the reaction, chloroplatic acid was dissolved in tetrahydrofuran and isoropanol. After the reaction was carried out at 90℃for 3 hours, the silyl-terminated polyether with silyl introduction rate of 78% was obtained. Moreover, the H1NMR spectra indicated that the silyl-terminated polyether with a little remnants terminal allyl prepared in this paper was better than the sample of Kaneka Corporation.更多还原