HDI制备过程中副产物水解氯生成机理实验研究

doi:10.11949/0438-1157.20241092

摘要/Abstract

摘要：

六亚甲基二异氰酸酯（HDI）是一种重要的化学品，主要通过己二胺与光气之间的光气化反应合成。在异氰酸酯产品中，水解氯的含量是衡量其质量的关键指标之一，对产品的稳定性和性能具有举足轻重的影响。深入探讨HDI制备过程中副产物水解氯的生成机理，细致分析了氧气含量、加热时间以及过热温度等因素对水解氯种类及含量的具体影响，并据此提出了相应的控制策略。实验结果显示，胺溶液中氧气的存在对己二胺影响显著，氧气在胺受热过程中加速了水解氯的生成。因此，对胺溶液进行除氧预处理，可有效减少水解氯的生成量。同时，在确定己二胺的过热温度时，需在可接受的水解氯含量范围与避免设备堵塞现象之间进行合理权衡，力求在不引发设备堵塞的前提下，最大限度地减少水解氯的生成。

关键词: 六亚甲基二异氰酸酯, 氧气, 反应时间, 过热温度, 水解氯

Abstract:

Hexamethylene diisocyanate (HDI) is a pivotal chemical primarily synthesized through the photogasification reaction of hexamethylenediamine and phosgene. In isocyanate products, the content of hydrolyzed chlorine serves as a vital indicator for quality control, significantly impacting the product's stability and performance. This study delves into the formation mechanism of hydrolyzable chlorine by-products during the preparation of HDI. We analyzed the influence of oxygen content, heating time, and superheating temperature on the types and quantities of hydrolyzable chlorine, and subsequently proposed corresponding control strategies. Experimental results reveal that oxygen in the amine solution notably affects ethylenediamine. Specifically, during the heating process, oxygen accelerates the formation of hydrolyzed chlorine. Pretreatment of the amine solution to remove oxygen can effectively mitigate the formation of hydrolyzed chlorine. Additionally, the superheating temperature of hexamethylenediamine should be carefully balanced between acceptable levels of hydrolyzed chlorine and the risk of equipment blockage, thereby minimizing the production of hydrolyzed chlorine without causing equipment issues.

Key words: hexamethylene diisocyanate, oxygen, reaction time, overheating temperature, hydrolyzed chlorine

中图分类号:

TQ 032.4

毛建拥, 葛纪军, 徐盼, 毕荣山. HDI制备过程中副产物水解氯生成机理实验研究[J]. 化工学报, 2025, 76(S1): 384-392.

Jianyong MAO, Jijun GE, Pan XU, Rongshan BI. Experimental study on the formation mechanism of hydrolyzed chlorine as a by-product during HDI preparation[J]. CIESC Journal, 2025, 76(S1): 384-392.

图/表 9

表1 实验原料和纯度

Table 1 Sources and purities of experimental materials

分子式	化学名称	CAS号	供应商	纯度/% (质量分数)
C₆H₁₆N₂	己二胺	124-09-4	英威达尼龙化工(中国)有限公司	99.90
CH₄O	甲醇	67-56-1	—	99.80
C₃H₆O	丙酮	67-64-1	—	99.80
N₂	氮气	7727-37-9	—	—
AgNO₃	硝酸银	7761-88-8	—	99.80
NaCl	氯化钠	7647-14-5	—	99.80
COCl₂	光气	75-44-5	山东新和成股份有限公司	—

图1 胺溶液受热实验装置图

Fig.1 Experimental device diagram of amine solution heating

图2 HDI中试生产路线

Fig.2 HDI pilot production route

图3 胺溶液分别在正常加热(a)、通入空气中加热(b)和除氧加热(c)反应后产品的气相色谱图

Fig.3 The gas chromatograms of the products after the reaction of amine solution in normal heating (a), heating in air (b) and deoxygenation heating (c) were obtained respectively

图4 中试生产中不除氧和除氧条件下HDI产品的气相色谱图

Fig.4 Gas chromatogram of HDI products without/with oxygen in pilot production

图5 不同氧气含量环境中反应时间对3,4,5,6-四氢-2H-氮杂卓/己二胺含量的影响

Fig.5 The effect of reaction time on the content of 3,4,5,6-tetrahydro-2H-azepine/hexamethylenediamine in different oxygen content environment

图6 预除氧/无除氧条件下反应时间对2,3,4,5-四氢-1H-氮杂卓-1-羰基氯含量的影响

Fig.6 Effect of reaction time on the content of 2,3,4,5-tetrahydro-1H-azepin-1-carbonyl chloride under pre-deoxygenation / deoxygenation conditions

图7 不同过热温度下HDI产品的气相色谱图

Fig.7 The gas chromatograms of HDI products at different superheating temperatures

图8 过热温度对杂质含量的影响

Fig.8 Effect of overheating temperature on impurity content

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