申请人:THE FIRESTONE TIRE & RUBBER COMPANY
公开号:EP0002196A1
公开(公告)日:1979-06-13
Polymers of anionically polymerized monomers such as mono-olefins, conjugated dienes, vinyl substituted aromatics, vinyl substituted pyridine, vinyl substituted quinolines, various aldehydes, various epoxides. various oxetanes, various oxygen-containing compounds, and the like are produced and end capped witb a polyisocyanate. or polyisothiocyanate having the formula R(N=C=X)n wherein R is a hydrocarbon, n is 2 or 3, and X is oxygen or sulfur. Such end capped polymers, of course, contain one reacted or connected isocyanate or isothiocyanate group and at least one free isocyanate or isothiocyanate end group, which free end group(s) reacts with an amide to give an imide end group. The imide terminated polymer is then hydrolyzed to form a stable amine terminated polymer. The reaction of the amide compound with the isocyanate(s) or isothiocyanate(s), followed by hydrolysis, results in the replacement of the free isocyanate or isothiocyanate end group(s) with an amine group(s). Thus, the amine terminated polymer contains the polymer connected to an isocyanate or isothiocyanate group (now an amide group or a thioamide group), which in turn is attached to the hydrocarbon portion, that is, the "R" portion of the polyisocyanate, which in turn is connected to the formed amine group. The amine terminated polymers may be stored extended periods of time and then reacted with various polymers, prepolymers, monomers, or various combinations thereof to form various block or graft copolymers. That is, the amine terminated polymer may be subsequently reacted with any amine reactive compound such as diepoxy monomers or an epoxy prepolymer in the presence of known epoxy catalysts to give a blocked epoxy copolymer. Similarly, the amine terminated polymer may be reacted with urea prepolymers or urea-forming monomers to yield a block urea copolymer. Reaction of the amine terminated polymer with urethane polymers, urethane prepolymers, or urethane-forming monomers will yield a urethane block copolymer. Reaction of the amine terminated polymer with urethane-urea prepolymers or urethane-urea forming monomers will yield a urethane-urea block copolymer. Similarly, various dianhydride and diamine monomers may be utilized to form an imide block copolymer.
生产阴离子聚合单体(如单烯烃、共轭二烯、乙烯基取代的芳烃、乙烯基取代的吡啶、乙烯基取代的喹啉、各种醛、各种环氧化物、各种氧杂环丁烷、各种含氧化合物等)的聚合物,并用具有式 R(N=C=X)n 的多异氰酸酯或多异硫氰酸酯封端,其中 R 是烃,n 是 2 或 3,X 是氧或硫。当然,这种末端封端的聚合物包含一个已反应或连接的异氰酸酯或异硫氰酸酯基团和至少一个游离的异氰酸酯或异硫氰酸酯末端基团,游离的末端基团与酰胺反应生成亚胺末端基团。然后,酰亚胺端基聚合物水解形成稳定的胺端基聚合物。酰胺化合物与异氰酸酯或异硫氰酸盐反应后水解,游离的异氰酸酯或异硫氰酸盐端基会被胺基团取代。因此,胺封端聚合物含有与异氰酸酯或异硫氰酸酯基团(现为酰胺基团或硫代酰胺基团)相连的聚合物,而异氰酸酯或异硫氰酸酯基团又与多异氰酸酯的烃部分,即 "R "部分相连,而 "R "部分又与形成的胺基团相连。胺封端聚合物可长期储存,然后与各种聚合物、预聚物、单体或其各种组合反应,形成各种嵌段或接枝共聚物。也就是说,胺封端聚合物随后可以在已知环氧催化剂的存在下,与任何胺活性化合物(如二环氧单体或环氧预聚物)反应,生成嵌段环氧共聚物。同样,胺封端聚合物也可与脲预聚物或脲形成单体反应,生成嵌段脲共聚物。胺封端聚合物与氨基甲酸乙酯聚合物、氨基甲酸乙酯预聚物或氨基甲酸乙酯形成单体反应,可生成氨基甲酸乙酯嵌段共聚物。胺封端聚合物与氨基甲酸乙酯-尿素预聚物或氨基甲酸乙酯-尿素形成单体反应将产生氨基甲酸乙酯-尿素嵌段共聚物。同样,各种二酐和二胺单体也可用于形成酰亚胺嵌段共聚物。