SYNTHESES OF POLYMER-BOUND RHODIUM COMPLEXES AND THEIR APPLICATION AS CATALYSTS FOR THE HYDROFORMYLATION OF DIISOBUTYLENE (Ⅰ)

Copolymer of styrene-divinylbenzene in bead form (with DVB 8%, average pore radius 3.0×10~2, specific surface area 25m~2/g, particle size 0.2—0.4mm) was made by the suspension polymerization. After chloromethylation, the beads were then reacted with lithium diphenyl phosphine and various amines separately. Two types of polymeric ligands, i.e. polyvinylbenzyl diphenyl phosphine and eight kinds of polyvinylbenzyl amines were thus obtained. In order to prepare the polymer-bound rhodium complexes, the ligands were then reacted with [Rh(CO)_2CI]_2. The initial composition and structure of the polymeric complexes were verified by IR spectra. The complexes synthesized above were used to catalyze the hydroformylation of diisobutylene under conditions of 110℃, 100(120) kg/cm~2 and H_2/CO=1:1. The effects of the donor atoms (N, P) on the activity of the two types of catalysts and the N-substituted groups on the activity 'of polymeric amine-rhodium complexes were examined.     

几种新型聚合物配体的合成及其固载化铑催化剂的醛化性能研究

本文使用交联聚苯乙烯为载体合成了几种新型的聚合物配体和固载化铑催化剂,考察了它们对二异丁烯和戊烯-1氢甲酰化反应的催化性能,探讨了催化剂的铑脱落现象。     

聚合物负载铑催化剂的稳定性研究—三氯化镧的影响

本文研究了聚合物负载铑催化剂引入三氯化镧后在氢甲酰化反应中的催化活性和稳定性,发现在大多数实验条件下,镧的引入对聚合物负载铑催化剂的性能有较大影响。     

SYNTHESES OF POLYMERIC LIGAND-BOUND RHODIUM COMPLEXES AND THEIR CATALYTIC APPLICATION FOR THE HYDROFORMYLATION OF DIISOBUTYLENE

Ten polymeric ligand bound rhodium complexes were synthesized by the reaction ofRh_2(CO)_4Cl_2 and functional cross-linked poly-styrene consisting of amine, aminophosphine andphosphite groups. These polymeric catalysts were used for hydroformylation of diisobuty-lene at a temperature of 110℃, under pressures of 100, 80, 60 kg/cm~2 and H_2/CO = 1: 1 for 6h, benzene being used as the solvent. Most of the catalysts prepared showed good catalyticproperties. IR spectral analysis indicates that the polymeric amine bound rhodium catalystspossess a polydentatc structure. The rhodium elution of the catalysts was examined. Therelationship between the structure of ligands, the rhodium elution and catalytic activity wasdiscussed. A curve of rhodium elution v.s. the number of catalytic application cycles wasinvestigated. The influence of reaction conditions and additives on the loss of rhodium wasalso studied. The possible mechanism of rhodium elution of the polymeric catalysts wassuggested.     

聚合物键铑络合物的合成及其在催化二异丁烯氢甲酰化反应中的应用

苯乙烯、二乙烯基苯经悬浮共聚制成珠状、大孔共聚体(交联度8％,孔径r=3.0×10~2,比表面积25M~2/g,粒度0.2—0.4mm),再经氯甲基化、膦化或胺化等功能基反应制成聚乙烯苄基二苯基膦和八种聚乙烯苄胺树脂。用这些聚合物配位体和二-μ-氯四羰基二铑[Rh_2(CO)_4Cl_2]反应,制成九种聚合物键铑催化剂。测定了二-μ-氯四羰基二铑、九种聚合物配位体和聚合物键铑催化剂的红外光谱。比较了聚合物膦、胺二类配体催化剂的活性及N-取代基对聚合物苄胺-铑催化剂活性的影响。     

聚合物配位体络铑催化剂的合成及对二异丁烯氢甲酰化反应的催化性能研究

本文用含有多胺、多(胺基膦)和单齿的胺基膦、亚磷酸酯等配位基团的功能基化交联聚苯乙烯与二氯四羰基二铑反应得到了10种聚合物配位体络铑催化剂。用这些催化剂进行了二异丁烯的催化氢甲酰化反应(反应条件:110℃;100,80,60kg/cm~2;H_2/CO=1:1;6h;苯为溶剂),大多数催化剂表现出了良好的催化性能。催化剂的红外光谱证明了聚合物多胺配位体与铑活性中心之间具有多齿配位结构。文中还对催化过程的铑脱落现象进行了研究,讨论了配位体结构与铑脱落量及催化活性的关系,测定了铑脱落量与催化剂使用次数关系的曲线,考察了反应条件及外添加试剂对铑脱落的影响,并提出了催化剂可能的铑脱落机制。     

载体及活性组份对聚合物负载铑络合物的催化醛化性能和稳定性的影响

本文研究了载体和活性组份(包括载体交联度、孔径、比表面及铑负载量等因素)对聚合物负载铑络合物在己烯-1氢甲酰化反应中的催化性能与稳定性的影响。