Polyketones

Abstract

Aliphatic polyketones are a new family of polymers obtained by the palladium(II)‐catalyzed, perfectly alternating copolymerization of CO and olefins. Various aspects of polyketone catalysis, the polymerization process, the types and properties of polyketones, and their applications are reviewed, with special emphasis on commercial grades of CO/ethene/propene‐based terpolymer, a new semicrystalline engineering thermoplastic.

Terpolymerisation of 1-olefin and ethene with CO catalysed by the [PdCl2(dppp)] complex in methanol as a solvent [dppp=1,3-bis(diphenylphosphino)propane]

“…Quite interesting, the productivities are very close to the values reported in literature for terpolymerisations catalysed by Pd(II)-(dppp) complexes having weakly coordinating ligands [6].…”

Palladium-Catalyzed Homo- and Copolymerization of Polar Monomers: Synthesis of Aliphatic and Aromatic Polymers

“…104 In polymer chemistry, the copolymerization of ethylene with different comonomers under transition metal catalysis is an effective method to synthesize a wide range of industrial copolymers, including linear low-density polyethylene (LLDPE), 105 cyclic olefin copolymers (COCs), 106,107 and aliphatic polyketones. 108,109 However, the use of arynes and their congeners for the introduction of o-arylene linkages into linear polyethylene has not been explored. Thus, we decided to Since [2.2.1]oxabicyclic alkenes are cyclic allylic ethers, it is necessary to use transition metal catalysts that can promote the polymerization of both polar monomers and ethylene.…”

Terpolymerization of propene and ethene with carbon monoxide catalyzed by [PdCl2(dppf)] in HCOOH–H2O as a solvent [dppf=1,1′-bis(diphenylphosphino)ferrocene]

“…Pd(II)-chelating diphosphine complexes efficiently catalyze the strictly alternating co-and ter-polymerization of CO with aliphatic 1-olefins, providing access to a new family of engineering thermoplastics named polyketones (PK) [1][2][3].…”

“…In contrast to the intensive efforts devoted to ethene (E)-carbon monoxide (ECO) copolymerization, much less has been reported on terpolymerization of two olefins with carbon monoxide [1][2][3][4][5][6][7][8][9][10][11][12], although industries have shown more interest for terpolymers than for copolymers, as documented by the high number of patents in this field. This is because the ECO copolymer is a highly crystalline material with high melting point (T m ), whereas the terpolymers have lower melting points, making them more easily processable [13][14][15][16][17][18][19].…”

“…Among the main aspects that rule the Pd(II)-catalysis the nature of the chelating ligand, of the counter-anion and of the solvent plays a key role [1][2][3][22][23][24][25]. Methanol is the most used solvent in which case the counter-anions must be weakly coordinating in order to ensure high productivity.…”