申请人:GULF RESEARCH & DEVELOPMENT COMPANY
公开号:EP0046328A1
公开(公告)日:1982-02-24
Ethylene is oligomerized by reacting ethylene in methanol under oligomerization conditions in contact with a nickel ylide defined by the following Formula I:
wherein R,, R2, R3, R4, Rs, R6, R7 and Ra are either alike or different members selected from the group consisting of hydrogen, alkyl radicals having from about one to about 24 carbon atoms, preferably from about one to about 10 carbon atoms; aryl radicals having from about six to about 20 carbon atoms, preferably from about six to about 10 carbon atoms; alkenyl radicals having from about two to about 30 carbons atoms, preferably from about two to about 20 carbon atoms; cycloalkyl radicals having from about three to about 40 carbon atoms, preferably from about three to about 30 carbon atoms; aralkyl and alkaryl radicals having from about six to about 40 carbon atoms, preferably from about six to about 30 carbon atoms; a halogen radical selected from the group consisting of fluorine, chlorine, bromine and iodine, preferably chlorine; a hydroxyl group; an alkoxy or aryloxy group; and a hydrocarbyl group, such as defined above, carrying halogen, hydroxyl or alkoxy or aryloxy; provided that at least one, preferably from about one to about four, of each of R, to Rs is a sulfonato group (-SO3- ) or an alkyl, aryl, alkenyl, cycloalkyl, aralkyl or alkaryl group carrying a sulfonato group; M is sulfur or oxygen, preferably oxygen; E is phosphorus, arsenic, antimony or nitrogen, preferably phosphorus; and F is phosphorus; arsernic or antimony, preferably phosphorus. There is thus obtained a reaction product containing (A) a methanol phase having dissolved therein the nickel ylide catalyst and (B) an alpha olefin phase. These two phases are then separated from each other to recover the alpha olefin phase. The use of methanol as the solvent medium causes the reaction product to resolve itself into two phases, an upper phase containing most of the oligomer product and a lower methanol phase carrying the catalyst dissolved therein. This permits easy separation of the product from the reaction mixture and also permits effective recycle of methanol with dissolved catalyst. The product obtained contains normal alpha olefins having from about four to about 100 carbon atoms, generally from about four to about 50 carbon atoms.
在低聚条件下,
乙烯在
甲醇中与由下式 I 定义的
镍酰亚胺发生反应,从而使
乙烯低聚:
其中 R、R2、R3、R4、Rs、R6、R7 和 Ra 是相同或不同的成员,选自氢、具有约 1 至约 24 个碳原子(最好是约 1 至约 10 个碳原子)的烷基、具有约 6 至约 20 个碳原子(最好是约 6 至约 10 个碳原子)的芳基组成的组;具有约 2 至约 30 个碳原子,最好是约 2 至约 20 个碳原子的烯基; 具有约 3 至约 40 个碳原子,最好是约 3 至约 30 个碳原子的环烷基; 具有约 6 至约 40 个碳原子,最好是约 6 至约 30 个碳原子的芳基和烷芳基;从
氟、
氯、
溴和
碘(最好是
氯)组成的组中选出的卤素基;羟基;烷氧基或芳氧基;以及烃基,如上文所定义的,带有卤素、羟基或烷氧基或芳氧基的烃基;条件是 R、Rs 至 Rs 中至少有一个(最好是约一个至约四个)是磺酰基(-SO3-)或带有磺酰基的 烷基、芳基、烯基、环烷基、芳基或烷芳基;M 是
硫或氧,最好是氧;E 是
磷、
砷、
锑或氮,最好是
磷;F 是
磷、
砷或
锑,最好是
磷。这样就得到了一种反应产物,其中包含(A)
甲醇相(其中溶解了
镍催化剂)和(B)α-烯烃相。然后将这两相分离,回收α-烯烃相。使用
甲醇作为溶剂介质可使反应产物分解成两相,上相含有大部分低聚物产物,下相为
甲醇相,其中溶解有催化剂。这样就可以很容易地从反应混合物中分离出产物,还可以有效地回收
甲醇和溶解的催化剂。得到的产品含有碳原子数从 4 个到 100 个不等的普通α-烯烃,碳原子数一般从 4 个到 50 个不等。