【作者】 黄莹莹；

【导师】 吴嘉麟；

【作者基本信息】 东华大学 ， 材料科学与工程， 2007， 硕士

【摘要】 由于现今石油危机的出现，世界各国都在寻找能代替石油和天然气的原料，而利用数量巨大的可再生的生物资源转化和生产新型能源、新材料以及各种化工产品，对维护人类繁衍和未来社会可持续发展有着划时代的意义。由吉林长春大成集团生产的玉米化工多组分二元醇含有乙二醇、1，2-丙二醇、1，2-环戊二醇等二元醇，可代替石油化工二元醇制备共聚酯，从而为这种可再生生物资源提供了广阔应用的可能性。本课题正是以有效利用多组分二元醇制备共聚酯为目的，探索混合醇酯化及缩聚的工艺条件，研究共聚酯的性能，使这种生物化工原料能在现有的工业设备及技术条件下，用于大规模的聚酯生产。用气相色谱-质谱联用技术分析了玉米化工乙二醇、1，2-丙二醇、多组分二元醇的成分。针对不同的二元醇，采用各种方法对其分别进行纯化，其中有活性炭脱色、萃取、电极处理、微波蒸馏等，并对纯化后的原料进行测试对比。微波蒸馏法能较有效去除低沸点杂质，增加二元醇的相对含量，其中玉米化工乙二醇从原来相对含量为89.176％增加到96.214％。探索了不同催化剂及不同用量情况下产品的质量，不同温度条件下酯化反应效率。通过对酯化馏出物的分析确定不同酯化转化率，研究多种二元醇参与的酯化与乙二醇酯化的不同点。根据馏出物排出体积，玉米化工乙二醇（含少量1，2-丙二醇）在高温阶段酯化馏出物体积增长较快，但是对馏出物进行分析，发现高温阶段乙二醇蒸出较多，而酯化生成的水都是在200～230℃左右馏出。而多组分二元醇则以较稳定的速率进行，反应时间较长，在加入纳米SiO₂后，反应时间缩短，但不明显，而缩聚时间明显减少。用红外光谱和核磁共振研究了聚合物的结构，结果显示二元醇比例与高分子链中的比例基本一致，说明共聚成功。用DSC仪研究了共聚酯的热性能，发现多组分二元醇共聚酯的低温结晶能力较强，但是熔点较低。研究了共聚酯的流变行为以确定其成纤能力。流动曲线结果显示玉米化工乙二醇共聚酯的流动性能佳，1g^σ-1g^γ关系曲线表明其分子量分布比普通乙二醇要窄，这有利于成型之后纤维的强度及条干均匀度。更多还原

【Abstract】 Nowadays, in a looking for a substitute for oil and gas process, numerous regenerate biomaterials, new materials and chemical materials are become more and more popular. The transformation of these products into energy has huge impacts on the future sustainable development. The multi-component glycols produced by Dacheng Group including ethylene glycol, 1,2-propylene glycol, can be used to prepare co-polyester, which raise the application possibility of this regenerate biomaterials. In this paper, we used multi-component diols as the raw material for the polymerization; study the various factors on the polymerization process and the impact of multi-component glycols on polymer’s properties.GC-MS were used to character three raw materials composite we used. The result showed that the different purification method can achieve the different effect. Microwave distillation has the best effect and the raise the glycol concentration from 89.2% to 96.2%.The polymers were synthesized using different catalyst, different catalyst concentration and different temperature. The differences of polymerization between normal ethylene glycols and multi-component glycols were studied by analyzing the distillation of esterification. The reaction temperature of corn-chemical glycol happened in about 200-230℃, while the multi-component diols took more time to realize the esterification. But the reaction time was shorter after adding the nano-SiO₂.FTIR and NMR were used to analyze the polymer structure. The results showed that the polymer synthesized were target polymer. DSC was used to analyze the polymer thermo property. The results showed that co-polyester prepared by multi-component diols had better cold crystallization but lower melt point.更多还原