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A rapid and ecofriendly microwave assisted p-dodecylbenzenesulfonic acid (DBSA) emulsion polycondensation of long-chain suberin model comonomers was successfully carried out for the first time. Microwave irradiation reduced drastically the reaction time to only 15 min, compared with the DBSA/water polycondensation under conventional heating. Bulk polycondensation using CALB lipase or Bi(OTf)3 were also carried out with isolation yields up to 93% and number-average molecular weights up to around 7300.