Dataset Information

Keto-Polyethylenes with Controlled Crystallinity and Materials Properties from Catalytic Ethylene-CO-Norbornene Terpolymerization.

ABSTRACT: Recent advances in Ni(II) catalyzed, nonalternating catalytic copolymerization of ethylene with carbon monoxide (CO) enable the synthesis of in-chain keto-functionalized polyethylenes (keto-PEs) with high-density polyethylene-like materials properties. Addition of norbornene as a bulky, noncrystallizable comonomer during catalytic polymerization allows tuning of the crystallinity in these keto-PE materials by randomly incorporated norbornene units in the polymer chain, while molecular weights are not adversely affected. Such crystallinity-reduced keto-PEs are characterized as softer materials with better ductility and may therefore be more suited for, e.g., potential film applications.

SUBMITTER: De Stefano F

PROVIDER: S-EPMC10867887 | biostudies-literature | 2024 Feb

REPOSITORIES: biostudies-literature

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Keto-Polyethylenes with Controlled Crystallinity and Materials Properties from Catalytic Ethylene-CO-Norbornene Terpolymerization.

De Stefano Fabio F Baur Maximilian M De Rosa Claudio C Mecking Stefan S

Macromolecules 20240112 3

Recent advances in Ni(II) catalyzed, nonalternating catalytic copolymerization of ethylene with carbon monoxide (CO) enable the synthesis of in-chain keto-functionalized polyethylenes (keto-PEs) with high-density polyethylene-like materials properties. Addition of norbornene as a bulky, noncrystallizable comonomer during catalytic polymerization allows tuning of the crystallinity in these keto-PE materials by randomly incorporated norbornene units in the polymer chain, while molecular weights ar ...[more]

PMID: 38370911

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Project description:Polyolefins account for 60% of global plastic consumption, but many potential applications of polyolefins require that their properties, such as compatibility with polar polymers, adhesion, gas permeability, and surface wetting, be improved. A strategy to overcome these deficiencies would involve the introduction of polar functionalities onto the polymer chain. Here, we describe the Ni-catalyzed hydroxylation of polyethylenes (LDPE, HDPE, and LLDPE) in the presence of m CPBA as an oxidant. Studies with cycloalkanes and pure, long-chain alkanes were conducted to assess precisely the selectivity of the reaction and the degree to which potential C-C bond cleavage of a radical intermediate occurs. Among the nickel catalysts we tested, [Ni(Me4Phen)3](BPh4)2 (Me4Phen = 3,4,7,8,-tetramethyl-1,10-phenanthroline) reacted with the highest turnover number (TON) for hydroxylation of cyclohexane and the highest selectivity for the formation of cyclohexanol over cyclohexanone (TON, 5560; cyclohexanol/(cyclohexanone + ε-caprolactone) ratio, 10.5). The oxidation of n-octadecane occurred at the secondary C-H bonds with 15.5:1 selectivity for formation of an alcohol over a ketone and 660 TON. Consistent with these data, the hydroxylation of various polyethylene materials by the combination of [Ni(Me4Phen)3](BPh4)2 and m CPBA led to the introduction of 2.0 to 5.5 functional groups (alcohol, ketone, alkyl chloride) per 100 monomer units with up to 88% selectivity for formation of alcohols over ketones or chloride. In contrast to more classical radical functionalizations of polyethylene, this catalytic process occurred without significant modification of the molecular weight of the polymer that would result from chain cleavage or cross-linking. Thus, the resulting materials are new compositions in which hydroxyl groups are located along the main chain of commercial, high molecular weight LDPE, HDPE, and LLDPE materials. These hydroxylated polyethylenes have improved wetting properties and serve as macroinitiators to synthesize graft polycaprolactones that compatibilize polyethylene-polycaprolactone blends.

Project description:The ethylene/norbornene content within cyclic olefin copolymer (COC) is well known to affect the chemical and physical properties of the copolymer, such as the glass transition temperature (Tg) and transparency. However, no work has been reported evaluating the effects of the ethylene/norbornene content on the surface properties of COC following UV/O3 or O2 plasma activation. Activation with either O2 plasma or UV/O3 is often used to assist in thermal assembly of fluidic devices, increasing the wettability of the surfaces, or generating functional scaffolds for the attachment of biological elements. Thus, we investigated differences in the physiochemical surface properties of various ethylene/norbornene compositions of COC following activation using analytical techniques such as water contact angle (WCA), ATR-FTIR, XPS, TOF-SIMS, UV-VIS, AFM and a colorimetric assay utilizing Toluidine Blue O (TBO). Results showed that increased norbornene content led to the generation of more oxygen containing functionalities such as alcohols, ketones, aldehydes and carboxyl groups when activated with either UV/O3 or O2 plasma. Specifically, COC with ∼60% norbornene content showed a significantly higher -COOH functional group density when compared to COC with a 50% norbornene content and COC with a 35% norbornene content following UV/O3 or O2 plasma activation. Furthermore, COC with large norbornene contents showed a smaller average RMS roughness (0.65 nm) when compared to COC containing low norbornene contents (0.95 nm) following activation making this substrate especially suited for nanofluidic applications, which require smooth surfaces to minimize effects arising from dielectrophoretic trapping or non-specific adsorption. Although all COC substrates showed >90% transparency at wavelengths >475 nm, COC possessing high norbornene contents showed significantly less transparency at wavelengths below 475 nm following activation, making optical detection in this region difficult. Our data showed distinct physiochemical differences in activated COC that was dependent upon the ethylene/norbornene content of the thermoplastic and thus, careful selection of the particular COC grade must be considered for micro- and nanofluidics.

Dataset Information

Keto-Polyethylenes with Controlled Crystallinity and Materials Properties from Catalytic Ethylene-CO-Norbornene Terpolymerization.

Publications

Keto-Polyethylenes with Controlled Crystallinity and Materials Properties from Catalytic Ethylene-CO-Norbornene Terpolymerization.

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