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    • 21. 发明授权
    • Process for the oligomerization of ethylene
    • 乙烯低聚方法
    • US4293727A
    • 1981-10-06
    • US179076
    • 1980-08-18
    • David L. BeachJames J. Harrison
    • David L. BeachJames J. Harrison
    • C07C2/32B01J31/00B01J31/18B01J31/22B01J31/24C07B61/00C07C1/00C07C2/36C07C11/02C07C67/00C07F15/04C08F110/02C07C2/02
    • B01J31/2404B01J31/1895B01J31/2247C07C2/36C07F15/04C08F110/02B01J2231/20B01J2531/847B01J2540/32C07C2531/24
    • Ethylene is oligomerized by contacting ethylene under oligomerization conditions with a nickel ylide defined by the following Formula I: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.8 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.sub.1 to R.sub.8 is a sulfonato group (--SO.sub.3.sup.-) 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, arsenic or antimony, preferably phosphorus. This process is characterized by a relatively high reaction rate at low temperatures and pressures and results in the production of relatively high proportions of desirable trimer, tetramer, pentamer, and higher olefinic products.
    • 乙烯通过在低聚条件下与乙烯接触,通过下列通式I所定义的镍叶立德使其低聚:其中R1,R2,R3,R4,R5,R6,R7和R8是相同或不同的成员, 的氢,具有约1至约24个碳原子,优选约1至约10个碳原子的烷基; 具有约6至约20个碳原子,优选约6至约10个碳原子的芳基; 具有约2至约30个碳原子,优选约2至约20个碳原子的烯基; 具有约3至约40个碳原子,优选约3至约30个碳原子的环烷基; 具有约6至约40个碳原子,优选约6至约30个碳原子的芳烷基和烷芳基; 选自氟,氯,溴和碘的卤素,优选氯; 羟基; 烷氧基或芳氧基; 和如上所定义的含有卤素,羟基或烷氧基或芳氧基的烃基; 条件是R 1至R 8中的至少一个,优选约1至约4个为磺酸基(-SO 3 - )或带有磺酸基的烷基,芳基,烯基,环烷基,芳烷基或烷芳基; M是硫或氧,优选氧; E是磷,砷,锑或氮,优选磷; F是磷,砷或锑,优选磷。 该方法的特征在于在低温和低压下的相对较高的反应速率,并导致产生相对较高比例的所需三聚体,四聚体,五聚物和更高级烯烃产物。