公开(公告)号：US20130079542A1

公开(公告)日：2013-03-28

申请号：US13239664

申请日：2011-09-22

申请人： Shenghong A. Dai ,  Xue-Yong Chen ,  Chao-Hsing Lin ,  Chun-Ying Huang ,  Wen-Chen Pan

发明人： Shenghong A. Dai ,  Xue-Yong Chen ,  Chao-Hsing Lin ,  Chun-Ying Huang ,  Wen-Chen Pan

IPC分类号： C07C269/04 ,  C07C273/02 ,  C07C263/04

CPC分类号： C07C263/04 ,  C07C269/04 ,  C08G18/7671 ,  C08G71/02 ,  C07C271/58 ,  C07C265/14

摘要： A preparation of aryl carbamates can be achieved readily by carbonylation of an aromatic polyamine compound with diphenyl carbonate (DPC) using a combination of an organic acid and a tertiary amine as a catalyst. Aryl carbamate can be converted into 4,4′-diphenylmethane diisocyanate (MDI) by heating it at about 200 to about 230° C. in a non-polar solvent containing inhibitor such as benzoyl chloride. In another application, trans-ureation of biscarbamates with an amine or mixed amines is found to be extremely facile in a polar solvent such as dimethyl sulfoxide (DMSO) and tetramethylene sulfone (TMS) in absence of any catalyst to make polyurea polymers of high molecular weights. Thus, efficient green-chemistry processes based on biscarbamates in making isocyanate products as well as urea prepolymers, urea elastomers and urea plastics have been developed in all in excellent yields without using reactive phosgene or 4,4′-diphenylmethane diisocyanate separately in the trans-ureation polymerizations.

摘要翻译： 通过使用有机酸和叔胺的组合作为催化剂使芳族多胺化合物与碳酸二苯酯（DPC）羰基化，可以容易地实现氨基甲酸芳基酯的制备。 通过在含有非极性溶剂的抑制剂如苯甲酰氯中将其加热至约200至约230℃，将氨基甲酸芳酯转化为4,4'-二苯基甲烷二异氰酸酯（MDI）。 在另一个应用中，发现在不存在任何催化剂的情况下，在极性溶剂如二甲基亚砜（DMSO）和四亚甲基砜（TMS）中，使用胺或混合胺转化双氨基甲酸酯非常容易地制备高分子量的聚脲聚合物 重量 因此，在制备异氰酸酯产物以及尿素预聚物，尿素弹性体和尿素塑料中基于双氨基甲酸酯的高效绿色化学方法已经以优异的产率开发，而不用在反式碳酸酯中分别使用反应性光气或4,4'-二苯基甲烷二异氰酸酯， 脲化聚合。

公开(公告)号：US09012676B2

公开(公告)日：2015-04-21

申请号：US13239664

申请日：2011-09-22

申请人： Shenghong A. Dai ,  Hsueh-Yung Chen ,  Chao-Hsing Lin ,  Chun-Ying Huang ,  Wen-Chen Pan

发明人： Shenghong A. Dai ,  Hsueh-Yung Chen ,  Chao-Hsing Lin ,  Chun-Ying Huang ,  Wen-Chen Pan

IPC分类号： C07C261/00 ,  C07C269/00 ,  C07C271/00 ,  C07C263/04 ,  C07C269/04 ,  C08G18/76 ,  C08G71/02

CPC分类号： C07C263/04 ,  C07C269/04 ,  C08G18/7671 ,  C08G71/02 ,  C07C271/58 ,  C07C265/14

摘要： A preparation of aryl carbamates can be achieved readily by carbonylation of an aromatic polyamine compound with diphenyl carbonate (DPC) using a combination of an organic acid and a tertiary amine as a catalyst. Aryl carbamate can be converted into 4,4′-diphenylmethane diisocyanate (MDI) by heating it at about 200 to about 230° C. in a non-polar solvent containing inhibitor such as benzoyl chloride. In another application, trans-ureation of biscarbamates with an amine or mixed amines is found to be extremely facile in a polar solvent such as dimethyl sulfoxide (DMSO) and tetramethylene sulfone (TMS) in absence of any catalyst to make polyurea polymers of high molecular weights. Thus, efficient green-chemistry processes based on biscarbamates in making isocyanate products as well as urea prepolymers, urea elastomers and urea plastics have been developed in all in excellent yields without using reactive phosgene or 4,4′-diphenylmethane diisocyanate separately in the trans-ureation polymerizations.

摘要翻译： 通过使用有机酸和叔胺的组合作为催化剂使芳族多胺化合物与碳酸二苯酯（DPC）羰基化，可以容易地实现氨基甲酸芳基酯的制备。 通过在含有非极性溶剂的抑制剂如苯甲酰氯中将其加热至约200至约230℃，将氨基甲酸芳酯转化为4,4'-二苯基甲烷二异氰酸酯（MDI）。 在另一个应用中，发现在不存在任何催化剂的情况下，在极性溶剂如二甲基亚砜（DMSO）和四亚甲基砜（TMS）中，使用胺或混合胺转化双氨基甲酸酯非常容易地制备高分子量的聚脲聚合物 重量 因此，在制备异氰酸酯产物以及尿素预聚物，尿素弹性体和尿素塑料中基于双氨基甲酸酯的高效绿色化学方法已经以优异的产率开发，而不用在反式碳酸酯中分别使用反应性光气或4,4'-二苯基甲烷二异氰酸酯， 脲化聚合。