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非光气合成1,6-己二异氰酸酯的清洁工艺研究
Alternative TitleStudy on the Non-phosgene Synthesis of 1, 6-Hexamethylene Diisocyanate
李新涛
Subtype博士
Thesis Advisor唐清
2013-05-01
Degree Grantor中国科学院研究生院
Degree Discipline环境工程
Keyword  6-己二异氰酸酯   1   6-己二胺   碳酸二甲酯   氨基甲酸甲酯   甲氧羰基化反应   动力学
AbstractCO2化工利用是绿色化学化工研究前沿。CO2经尿素转化为碳酸二甲酯(DMC)或氨基甲酸甲酯(MC),进一步与有机胺反应制备脂肪族异氰酸酯产品,不但可以替代传统光气路线,而且可以实现CO2的高值温和转化,是目前CO2化工利用技术研究的热点。本论文针对非光气合成高附加值脂肪族异氰酸酯-1, 6-己二异氰酸酯(HDI)的关键问题,以非均相催化体系为重点,分别探索由碳酸二甲酯、氨基甲酸甲酯合成中间体1, 6-己二氨基甲酸甲酯(HDC)以及HDC热解制备产品HDI工艺路线,创新性提出HDA和MC经两段变温反应工艺制备HDC以及HDC低沸点溶剂加压热解制备HDI工艺;深入开展催化剂筛选、催化反应机理、反应动力学和工艺条件优化研究,为非光气制备HDI工程化应用提供理论基础。主要研究内容和进展如下: (1)针对DMC和1, 6-己二胺(HDA)反应合成中间体HDC,基于均相催化剂,通过重结晶、柱层析等分离手段,明确反应过程中间体为1-(6-氨基)六亚甲基单氨基甲酸甲酯(HMC),主要的不可逆副产物为N-HDA、N-HMC和N,N-HMC,进而建立反应过程主副产物生成的反应网络;热力学分析表明,反应过程烷基化不可逆副反应易发生,应筛选更高效的催化剂。 (2)针对HDA和DMC反应过程,筛选出具有较高催化活性的AlSBA-15非均相催化剂,深入考察了催化剂负载量、反应温度、反应时间、摩尔配比、催化剂用量等工艺条件的影响规律。结果表明,在催化剂浓度5%,反应温度70℃,反应时间35h,DMC和HDA的摩尔比为6:1条件下,HDC的收率最高为84%;催化剂经过四次循环后,HDA的转化率和HDC的收率没有明显变化。 (3)采用原位红外技术,研究AlSBA-15催化HDA和DMC反应合成HDC过程的催化机理,发现催化剂和DMC有明显的相互作用,结合反应过程红外谱图的变化,推测催化剂中Al组份和DMC的羰基氧发生相互作用,导致其羰基对于的红外峰发生蓝移,因此提出了反应过程的加成消去机理;在催化反应机理研究基础上,建立反应过程的动力学模型,进一步分析表明中间体HMC和DMC反应生成HDC是整个过程的速控步骤,反应的指前因子为k0=2.64E+04mol-L (g?min)-1,反应活化能为E=45.7kJ/mol。 (4)开展氨基甲酸甲酯(MC)和HDA反应合成中间体HDC新工艺研究。创新性地提出两步变温反应工艺,大幅度抑制了聚脲副产物的生成。筛选出高活性的CeO2催化剂,在优化的条件下,HDC收率最高为87.7%,较一步反应工艺提高10%左右,聚脲物质选择性大幅度降低,仅为5.1%,其它副产物可以直接进入下一步热分解反应;催化剂经4次循环实验后,活性基本稳定,产物HDC收率没有明显变化。 (5)针对HDC热解制备HDI反应过程,创新性提出低沸点溶剂加压热解的新思路。采用热分析技术表明,HDC热解过程可分为HDC热解生成HDI、HDI聚合生成碳化二亚胺及HDI深度聚合三个阶段;动力学研究结果表明,HDC热分解机理函数为 ,反应活化能E=119.51kJ/mol,指前因子lgA=14.82 s-1;初步实验研究表明,采用Co2O3作为催化剂,在优化反应条件下,HDC转化率为100%,HDI收率达到89%,反应过程物料损失率约5%,优于目前报道的结果。
Other AbstractCO2 utilization is the frontier of green chemical. As important organic intermediates, dimethyl carbonate (DMC) and small molecular alkyl carbamate could be produced using CO2 as raw materials. Isocyanate, which is a high-value commodity chemical, can be synthesized by the reaction of amine with DMC or alkyl carbamate. This route not only implies a phosgene-free method for the synthesis of isocyanate, but also will utilization the CO2 in high efficiency under mild condition; therefore it has become a hot spot in the research of the CO2 transformation. In this paper, the key problems in the synthesis of 1, 6-hexamethylene-diisocyanate (HDI) by the reaction of hexamethylene diamine (HDA) and DMC or methyl carbamate (MC) was researched. The development of catalyst for the synthesis and decomposition of intermediate dimethylhexane-1, 6-dicarbamate (HDC), catalytic mechanism, reaction kinetics and technological conditions were studied. The achievements and progress were exhibited as follows: (1) The by-products and intermediate in the synthesis of HDC from HDA and DMC was investigated by using homogeneous catalyst. The compounds in the reaction aqueous were identified, and the results showed that methylated amine and carbamate were the main by-products.
Pages117
Language中文
Document Type学位论文
Identifierhttp://ir.ipe.ac.cn/handle/122111/8299
Collection研究所(批量导入)
Recommended Citation
GB/T 7714
李新涛. 非光气合成1,6-己二异氰酸酯的清洁工艺研究[D]. 中国科学院研究生院,2013.
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