申请人:UNION CARBIDE CORPORATION
公开号:EP0254277A2
公开(公告)日:1988-01-27
An oligomerization or cooligomerization process comprising passing ethylene or a mixture of ethylene and propylene in contact with a catalyst, in the liquid phase, said catalyst comprising the reaction product of (i) a transition metal compound wherein the transition metal is selected from the group consisting of nickel, chromium, cobalt, iron, and copper, and mixtures thereof; (ii) in the event that (a) the transition metal is not in the oxidation state of 0 or (b) the transition metal compound does not have a hydride or an alkyl, alkenyl, alkynyl, or aryl group bonded to the transition metal, a catalyst activator consisting of a compound capable of transferring a hydride or an alkyl, alkenyl, alkynyl, or aryl group from itself to the transition metal/ligand (hereinafter defined) complex formed by the reaction of the transition metal compound with the ligand and bonding the group to the transition metal, said activator being present in a sufficient amount to activate the catalyst; and (iii) at least one organophosphorus sulfonate ligand containing (a) at least one benzene ring having a trivalent phosphorus atom located at one position on the benzene ring and an SO3M group located at a position on the benzene ring ortho thereto, or at least one benzene ring having a trivalent phosphorus atom connected through a methylene group to a first position on the benzene ring and an SO3M group connected through a methylene group to a second position on the benzene ring ortho to the first position, or at least one bridging or fused aromatic ring system having a trivalent phosphorus atom and an 803M group, each located on a different aromatic ring in the system at substituent positions adjacent to one another, or at least one aromatic ring, other than a benzene ring, or heteroaromatic ring, each ring having a trivalent phosphorus atom and an S03M group located at substituent positions adjacent to one another, wherein M is selected from the group consisting of hydrogen, alkali metals, alkaline earth metals, and NR4 and PR4 wherein R is a hydrogen atom or a substituted or unsubstituted hydrocarbyl radical having 1 to 15 carbon atoms and each R can be alike or different or (b) a trivalent phosphorus atom connected through a group having the formula
to an SO3M group wherein A is an oxygen atom, an NH radical, or an NR radical; R2 and R3 are hydrogen atoms or a substituted or unsubstituted hydrocarbyl radical having 1 to 6 carbon atoms and can be alike or different; x is an integer 0 or 1; y is an integer from 1 to 3; and R and M are as defined above.
一种低聚或冷聚工艺,包括使
乙烯或
乙烯与
丙烯的混合物在液相中与催化剂接触,所述催化剂包括以下物质的反应产物:(i) 过渡
金属化合物,其中过渡
金属选自由
镍、
铬、
钴、
铁和
铜及其混合物组成的组;(ii) 在 (a) 过渡
金属的氧化态不是 0 或 (b) 过渡
金属化合物没有
氢化物或烷基、烯 基、炔基或芳基与过渡
金属键合的情况下,由能转移
氢化物或烷基、烯基、 烷基、炔基或芳基的化合物组成的催化剂活化剂、由能将
氢化物或烷基、烯基、炔基或芳基从自身转移到过渡
金属化合物与
配体反应并将该基团键合到过渡
金属上而形成的过渡
金属/
配体(以下定义)复合物的化合物组成,所述活化剂的存在量足以活化催化剂;(iii) 至少一种有机
磷磺酸盐
配体,其包含 (a) 至少一个苯环,该苯环上的一个位置有一个三价
磷原子,苯环上的一个位置有一个 SO3M 基团、或至少一个苯环,其三价
磷原子通过亚甲基连接到苯环上的第一位置,SO3M 基团通过亚甲基连接到苯环上与第一位置正交的第二位置;或至少一个桥接或融合芳环体系,其三价
磷原子和 803M 基团、或至少一个芳环(苯环除外)或杂芳环,每个环上都有一个三价
磷原子和一个 S03M 基团,它们的取代基位置彼此相邻、其中 M 选自氢、碱
金属、碱土
金属、NR4 和 PR4 所组成的组,其中 R 是氢原子或具有 1 至 15 个碳原子的取代或未取代的烃基,每个 R 可以相同或不同;或 (b) 三价
磷原子,通过具有以下式子的基团连接到 SO3M 基团上
其中 A 是氧原子、NH 自由基或 NR 自由基;R2 和 R3 是氢原子或具有 1 至 6 个碳原子的取代或未取代的烃基,每个 R 可以相同或不同;x 是 0 或 1 的整数;y 是 1 至 3 的整数;R 和 M 如上文所定义。