The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene‐bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting “off” and “on” behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. 相似文献
Summary: In non‐polar solvents such as toluene, Cp‐Ni and ‐Pd complexes (Cp = η5‐C5H5) with appropriate activators have been found to induce the addition polymerization of norbornene in excellent yields, for example (Cp)Pd(allyl)/[Ph3C][B(C6F5)4] gave 105 120 kg‐polymer/cat‐mol · h at room temperature. While the Cp‐Pd system was not suitable in the presence of ester‐substituted norbornenes, the Cp‐Ni system, for example (Cp)Ni(Cl)(PPh3)/AlMe3/B(C6F5)3 can copolymerize norbornene with 5‐norbornene‐2‐carboxylic acid methyl ester in toluene to give high yields (up to 68% in 2 h at room temperature) of copolymer with variable contents of the methyl ester monomer unit (17.4–60.7 mol‐%). These copolymers have high molecular weights ( = 234 100–109 500) and narrow molecular weight distributions ( = 1.78–1.89). In addition, they are soluble in common organic solvents giving flexible and transparent films on casting, that show very high Tg in the range of 352.8 to 316.0 °C. The same Ni‐catalyst system can also copolymerize norbornene derivatives with bulky substituents, i.e., 2‐butyl‐5‐norbornene and 5‐norbornene‐2‐carboxylic acid butyl ester. The Tg of these copolymers are lower (294.9–267.3 °C) than the methyl ester‐based copolymers, demonstrating that the Tg of the polynorbornene copolymer film can be tailored simply by changing the alkyl group of the monomer to within the range of 352 to 267 °C.
Figure showing the addition polymerization of norbornene using Cp‐Ni complex with appropriate activators. 相似文献
A model for olefin–diene copolymerization and long chain branch formation was developed. The model shows that the number‐average molecular weight and branching density increases linearly with time in a semi‐batch polymerization, while the polydispersity depends on the diene content in the polymer and on the polymerization time. For low diene fractions or low polymerization times, the polydispersity increases linearly with time. For higher diene contents, the polydispersity increases exponentially with polymerization time after a critical polymer concentration is reached. The calculated distributions of branched species indicate that diene content influences the amount of highly branched chains produced in the polymerization, markedly broadening the distribution of molecular weight and leading to gel formation.
Weight distribution of branched species after 30 min of polymerization. 相似文献
Seven Pd‐complexes with optically active bis[dihydroxazole]‐type ligands promote asymmetric alternating copolymerization of 7‐methylenebicyclo[4.1.0]heptane with CO, which produces an optically active polyketone, ? [C(?CH2)? CO? C6H10]n? . The reaction under increased CO pressure (> 5 atm) affords a polymer that contains monomer units with the cis‐cyclohexane‐1,2‐diyl group almost exclusively. The polyketone exhibits positive or negative optical rotation depending on the Pd‐complex. The highest and lowest [α] of the polymer obtained are + 68.9 and ? 76.1, respectively. Addition of dibutylcuprate to a solution of the polymer in the presence of Me3SiCl transforms the enone groups of the polymer to silyl enol ether groups, which are ozonized to (silyloxy)oxirane moieties. 相似文献
A series of sterically demanding α‐diimine ligands bearing electron‐donating and electron‐withdrawing substituents were synthesized by an improved synthetic procedure in high yield. Subsequently, the corresponding Pd complexes were prepared and isolated by column chromatography. These Pd complexes demonstrated unique properties in ethylene polymerization, including high thermal stability and high activity, thus generating polyethylene with a high molecular weight and very low branching density. Similar properties were observed for ethylene/methyl acrylate copolymerization. Because of the high molecular weight and low branching density, the generated polyethylene and ethylene/methyl acrylate copolymer were semicrystalline solids. The (co)polymers had unique microstructures originating from the unique slow‐chain‐walking activity of these Pd complexes. 相似文献
Summary: By a sidearm approach, a series of titanium complexes bearing an [O, N, S] tridentate ligand have been synthesized and proven to be highly active for ethylene polymerization. The complexes also show excellent ability to copolymerize ethylene with hex‐1‐ene and norbornene. The effects of the different sidearms on the catalytic behavior of the complexes were studied in detail.
The copolymerization of ethylene with hex‐1‐ene using titanium complexes bearing [O, N, S] tridentate ligands as catalysts. 相似文献
Room temperature ionic liquids (RTILs) as advanced, technological solvents can be designed to fit a particular application. They used as green “media and/or catalysts” for chemical synthesis have been extensively reviewed recently. RTILs1 not only show … 相似文献
The synthesis and single‐crystal X‐ray structures of the novel molybdenum imido alkylidene N‐heterocyclic carbene complexes [Mo(N‐2,6‐Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf)2] ( 3 ), [Mo(N‐2,6‐Me2C6H3)(IMes)(CHCMe2Ph)(OTf)2] ( 4 ), [Mo(N‐2,6‐Me2C6H3)(IMesH2)(CHCMe2Ph)(OTf){OCH(CF3)2}] ( 5 ), [Mo(N‐2,6‐Me2C6H3)(CH3CN)(IMesH2)(CHCMe2Ph)(OTf)]+ BArF? ( 6 ), [Mo(N‐2,6‐Cl2C6H3)(IMesH2)(CHCMe3)(OTf)2] ( 7 ) and [Mo(N‐2,6‐Cl2C6H3)(IMes)(CHCMe3)(OTf)2] ( 8 ) are reported (IMesH2=1,3‐dimesitylimidazolidin‐2‐ylidene, IMes=1,3‐dimesitylimidazolin‐2‐ylidene, BArF?=tetrakis‐[3,5‐bis(trifluoromethyl)phenyl] borate, OTf=CF3SO3?). Also, silica‐immobilized versions I1 and I2 were prepared. Catalysts 3 – 8 , I1 and I2 were used in homo‐, cross‐, and ring‐closing metathesis (RCM) reactions and in the cyclopolymerization of α,ω‐diynes. In the RCM of α,ω‐dienes, in the homometathesis of 1‐alkenes, and in the ethenolysis of cyclooctene, turnover numbers (TONs) up to 100 000, 210 000 and 30 000, respectively, were achieved. With I1 and I2 , virtually Mo‐free products were obtained (<3 ppm Mo). With 1,6‐hepta‐ and 1,7‐octadiynes, catalysts 3 , 4 , and 5 allowed for the regioselective cyclopolymerization of 4,4‐bis(ethoxycarbonyl)‐1,6‐heptadiyne, 4,4‐bis(hydroxymethyl)‐1,6‐heptadiyne, 4,4‐bis[(3,5‐diethoxybenzoyloxy)methyl]‐1,6‐heptadiyne, 4,4,5,5‐tetrakis(ethoxycarbonyl)‐1,7‐octadiyne, and 1,6‐heptadiyne‐4‐carboxylic acid, underlining the high functional‐group tolerance of these novel Group 6 metal alkylidenes. 相似文献