Higher α‐olefins carbonylation in aqueous media by Pd(II) catalysts modified with substituted diphosphine ligands: Aqueous polyketone latices with high solid contents and molecular weights

Abstract

Water‐soluble palladium complexes cis‐[Pd(L)(OAc)2] (1–8) (L represents a diphosphine ligands of the general formula CH2(CH2PR2)2, where for a: R  (CH2)6OH; b–g: R  (CH2)nP(O)(OEt)2, n = 2–6 and n = 8; h: R  (CH2)3NH2) have been employed, after activation with a large excess of HBF4, for emulsion polymerization of alkenes (propene, butene, and their equimolar mixtures) with carbon monoxide. Aliphatic polyketone lattices with a high solid content (21%), high molecular weight (6.3 × 104 g mol−1), and narrow polydispersities (Mw/Mn ≈ 2) were isolated. The catalytic activity of the dicationic palladium (II) based catalysts, C1–C8 is highly dependent on the length of the alkyl chain of the ligand. Catalyst 3 proved to be highly active for propene/CO copolymers, whereas 6 is active for butene/CO and propene/CO‐butene/CO systems. The presence of methyl β‐cyclodextrin, as a phase‐transfer agent, and undecenoic acid, as an emulsifier, increase the molar mass and the stability of the polyketones and finally the activity of the catalyst. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6715–6725, 2009

The Effect of Weakly Coordinating Solvent and Counter Anion on Diphosphine‐Palladium(II) Catalytic Reactivity for Copolymerization of 1‐Butene with Carbon Monoxide in Aqueous Media

“…of HBF 4 (12 ml 1 %); 20 g of 1-butene; 30 ml water with pH = 5.5; 0.15 g of emulsifier Texapon; total pressure 60 bar; reaction temperature 60 °C; reaction time 3 h; 0.15 g of methyl-β-cyclodextrin (W7 M 1.8); 1 g of undecenoic Acid. [11] Regarding the chain-length of the phosphorus ligands in (C1-C5), the highest catalytic activity was obtained at the longest alkyl chains (Table 1). The higher efficiency of the catalyst C5 in water is due to the ability of the long chain moiety to enhance the solubility of 1-butene gas in aqueous phase and the possibility for water to coordinate to the metal centre as ligand, which was demonstrated previously.…”

“…The synthesis and the characterization of the ligands (L1-L5) and complex (C6) were reported previously. [10,11] Polymer grade 1-butene, carbon monoxide were provided by BASF SE. Methyl-β-cyclodextrin (W7 M 1.8) and the Texapon® NSO (28 %) were purchased from Wacker-Chemie GmbH and Henkel GmbH, respectively.…”

Carbonylation of Ethene Catalysed by Pd(II)-Phosphine Complexes

“…The catalyst with n = 3 is highly active for the copolymerization with propene, whereas the one with n = 6 is active for CO-butene and CO-propene-butene polymerizations. The use of β-cyclodextrin, as a phase-transfer agent, and undecanoic acid, as an emulsifier, increase the stability of the PKs and the catalytic activity [130].…”

Effect of multi-walled carbon nanotubes aspect ratio and temperature on the dielectric behavior of alternating alkene-carbon monoxide polyketone nanocomposites

“…Furthermore, polymer properties such as crystallinity, stereochemistry, molecular weight, polarity, mechanical properties and thermal behavior can easily be tuned by the right choice of the monomer(s) and their ratio [31,32], type of catalyst [33][34][35], and reaction conditions [36]. For example, excellent elastic properties were obtained when the molar ratio of ethylene-carbon monoxide (E-CO) segments to the propylene-carbon monoxide (P-CO) in the terpolymer chain was less than 50%.…”