膦-磷酰胺型镍催化剂的制备及催化合成聚酮树脂  

Preparation of diphosphazane monoxide nickel catalysts for synthesis of polyketone resins

作　　者：杨建伟 李世环 陈世瑜 刘野 YANG Jianwei;LI Shihuan;CHEN Shiyu;LIU Ye(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China)

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁大连116024

出　　处：《精细化工》2025年第4期743-752,共10页Fine Chemicals

基　　金：国家自然科学基金项目(52273004)。

摘　　要：基于配体的电子调控策略,设计、合成了一系列膦-磷酰胺(PNPO)型镍配合物,采用1HNMR、13CNMR、HRMS对其进行了表征。将其用于催化乙烯/CO合成二元聚酮,探究了催化剂结构对催化剂转化数(即单位质量Ni制备的聚酮质量)、聚酮产量、数均相对分子质量(Mn)和相对分子质量分布的影响,并考察了最佳催化剂的反应条件。最后,将最佳催化剂用于催化乙烯、丙烯与CO的三元共聚反应。结果表明,催化剂转化数与聚酮的Mn随着配体膦端与氧化膦端的给电子能力的增强而升高,随着抗衡阴离子空间体积的增大而增加,膦端取代基与金属镍中心的弱配位相互作用对催化活性也有显著作用。胺端为N,N-二甲基对苯基、氧化膦端为二乙氨基、膦端为2,6-二甲氧基苯基、抗衡阴离子为四[3,5-双(三氟甲基)苯基]硼酸根离子的配合物(Ni15)具有最佳的催化乙烯/CO二元共聚反应的活性,在300 mL高压反应釜中,反应温度90℃、反应溶剂为二氯甲烷、V(C2H4)∶V(CO)=2∶1的最佳反应条件下,Ni15的转化数为15982 g/(g Ni),二元聚酮的Mn为234000。Ni15可催化乙烯、丙烯与CO的三元共聚反应,制备的三元聚酮丙烯插入率为4.3%,熔点(241℃)低于乙烯/CO二元聚酮的熔点(258℃)。A series of nickel coordinated diphosphazane monoxide(PNPO)complexes were designed and synthesized based on electronic modulation,characterized by 1HNMR,13CNMR and HRMS,and used to catalyze the synthesis of binary polyketones from ethylene/CO.The effect of catalyst structure on the turnover number(that is the mass of polyketone prepared per unit mass of Ni),the yield of polyketones,the number-average relative molecular mass(Mn)and relative molecular mass distribution of catalysts was investigated.The reaction conditions for the optimal catalyst were further explored,and the optimal catalyst was used to catalyze the terpolymerization of ethylene,CO with propylene.The results showed that an increase in the electron-donating nature at the phosphine and phosphine oxide moiety led to a progressive increase in the catalyst turnover number and Mn of polymer.The increase in the space at the counter-anions led to a progressive increase,and the weak interaction between the phosphorus and the metal-nickel also had a significant effect on the catalytic activity.Complex(Ni15)with an amine terminal of N,N-dimethyl p-phenyl,phosphine oxide terminal of diethylamino,phosphine terminal of 2,6-dimethoxyphenyl,counteranion of tetrakis[3,5-bis-(trifluoromethyl)phenyl]borate had the best catalytic activity of ethylene/CO binary copolymerization.The turnover number of Ni15 was 15982 g/(g Ni)and Mn of binary polyketone was 234000 in the 300 mL autoclave under the optimal reaction conditions of 90℃,dichloromethane as solvent and V(C2H4)∶V(CO)=2∶1.Ni15 could catalyze the terpolymerization of ethylene,propylene with CO,and the penetration rate of propylene was 4.3%,while the melting point(241℃)of ternary polyketone was lower than that of ethylene/CO binary polyketone(258℃).

关 键 词：配位聚合 镍系催化剂 聚酮 一氧化碳 乙烯 功能材料 

分 类 号：O631.5[理学—高分子化学] O643.36[理学—化学]