Polyketone materials: control of glass transition temperature and surface polarity by co‐ and terpolymerization of carbon monoxide with higher 1‐olefins

Abstract

Highly soluble alternating 1 -olefinkarbon monoxide copolymers with olefin monomers (H,C'CH-R) containing 4, 5, 6, 10, 14, 16 and 18 C-atoms in the R-substituents were prepared by the use of dicationic palladium(I1) phosphine catalysts and an optimized amount of methanol as activator. In terpolymerization experiments the influence of icosene-CO or octadecene-CO units, distributed randomly along a propene-CO or ethene-CO copolymer backbone, on molecular weight, glass transition temperature and on the surface polarity of films casted from solution has been investigated. As the length of the a-olefin side chain increases, the glass transition temperature (T,) of the copolymer is reduced from room temperature to almost -60 "C. For octadecene-CO and icosene-CO copolymers side chain crystallization occurs, leading to elastic materials. Contact angle measurements, performed on water drops located on the surface of selected co-and terpolymer films demonstrate the wide range of surface polarity which can be covered by simple copolymerization of polar CO groups with apolar alkenes.

Stretching calorimetry and X‐ray characterization of deformational behavior of new high molecular weight propene‐carbon monoxide alternating co‐ and terpolymers

“…These features make the new copolymers excellent vehicles for fundamental studies of structure -property relationships and allow to elucidate the role of crystallites on mechanical properties of such microheterogeneous polymer systems. Some correlation of copolymer composition with morphology and deformation behavior has been obtained using co-and terpolymers of carbon monoxide with higher 1-olefins 1,4) . When the molar ratio of ethene-CO to propene-CO in the terpolymer is less than 50%, the material reveals excellent elastic properties, while above this ratio the terpolymers are typical crystalline thermoplastics.…”

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

“…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]. As matter of fact, the first commercialized PK, was the propene (P)-ethene-CO (PECO) terpolymer (trade name CARILON ® by Shell [20] and KETONEX ® by BP [21]).…”

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]

“…When Hex concentration is higher than 4.5% (mol/mol), the decrease of LVN observed confirm point (ii) because the decrease of propagation rate favors also the termination step with formation of short polymer chain. On the other hand, the decrease of T m observed by increasing the Hex concentration, accords with a progressive increase of HexCO units along the polymer chain (or at the end) [3,54], also at low Hex concentration, where the productivity and LVN increase.…”