Abstract: The recent advances in the main clean processes to synthesize diphenylmethane diisocyanates (MDI) are reviewed，such as BTC method，condensation of aniline，reductive carbonylation of nitrobenzene，oxidative carbonylation of aniline，methoxycarbonylation of aniline，alcoholysis of N,N′-diphenyl urea and the coupling process. The coupling process not only has mild reaction conditions，simple operation，high atomic economy and low cost，but also promotes the mitigation and resource utilization of greenhouse gas CO2，and has the best commercialization prospect.

摘要： 回顾了清洁合成二苯甲烷二异氰酸酯（MDI）的几种主要方法，如BTC法、苯胺缩和法、硝基苯还原羰基化法、苯胺氧化羰基化法、碳酸酯法、二苯基脲法和反应耦合法等合成路线。其中反应耦合法不仅反应简单、条件温和、反应的原子经济性高、成本低，而且还可以推动温室气体CO2的减排和资源化利用，是一条比较有发展前景的非光气合成路线。