Dataset Information

Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer.

ABSTRACT: The direct synthesis of syndiotactic polystyrene-block-polyethylene copolymer (sPS-b-PE) with a diblock structure has been achieved. The synthetic strategy consists of the sequential stereocontrolled polymerization of styrene and ethylene in the presence of a single catalytic system: cyclopentadienyltitanium(IV) trichloride activated by modified methylaluminoxane (CpTiCl₃/MMAO). The reaction conditions suitable for affording the partially living polymerization of these monomers were identified, and the resulting copolymer, purified from contaminant homopolymers, was fully characterized. Gel permeation chromatography coupled with two-dimensional NMR spectroscopy COSY, HSQC, and DOSY confirmed the block nature of the obtained polymer, whose thermal behaviour and thin film morphology were also investigated by differential scanning calorimetry, powder wide angle x-ray diffraction, and atomic force microscopy.

SUBMITTER: Lamparelli DH

PROVIDER: S-EPMC6523272 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer.

Lamparelli David Hermann DH Speranza Vito V Camurati Isabella I Buonerba Antonio A Oliva Leone L

Polymers 20190416 4

The direct synthesis of syndiotactic polystyrene-block-polyethylene copolymer (sPS-<i>b</i>-PE) with a diblock structure has been achieved. The synthetic strategy consists of the sequential stereocontrolled polymerization of styrene and ethylene in the presence of a single catalytic system: cyclopentadienyltitanium(IV) trichloride activated by modified methylaluminoxane (CpTiCl<sub>3</sub>/MMAO). The reaction conditions suitable for affording the partially living polymerization of these monomers ...[more]

PMID: 30995818

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Project description:Nonpolar materials like polyolefins are notoriously challenging substrates for surface modification. However, this challenge is not observed in nature. Barnacle shells and mussels, for example, utilize catechol-based chemistry to fasten themselves onto all kinds of materials, such as boat hulls or plastic waste. Here, a design is proposed, synthesized, and demonstrated for a class of catechol-containing copolymers (terpolymers) for surface functionalization of polyolefins. Dopamine methacrylamide (DOMA), a catechol-containing monomer, is incorporated into a polymer chain together with methyl methacrylate (MMA) and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). DOMA serves as adhesion points, BIEM provides functional sites for subsequent "grafting from" reactions, and MMA provides the possibility for concentration and conformation adjustment. First, the adhesive capabilities of DOMA are demonstrated by varying its content in the copolymer. Then, terpolymers are spin-coated on model Si substrates. Subsequently, the atom transfer initiator (ATRP) initiating group is used to graft a poly(methyl methacrylate) (PMMA) layer from the copolymers, with 40% DOMA content providing a coherent PMMA film. To demonstrate functionalization on a polyolefin substrate, the copolymer is spin-coated on high-density polyethylene (HDPE) substrates. A POEGMA layer is grafted from the ATRP initiator sites on the terpolymer chain on the HDPE films to provide antifouling characteristics. Static contact angle values and Fourier transform infrared (FTIR) spectra confirm the presence of POEGMA on the HDPE substrate. Finally, the anticipated antifouling functionality of grafted POEGMA is demonstrated by observing the inhibition of nonspecific adsorption of the fluorescein-modified bovine serum albumin (BSA) protein. The poly(oligoethylene glycol methacrylate) POEGMA layers grafted on 30% DOMA-containing copolymers on HDPE show optimal antifouling performance exhibiting a 95% reduction of BSA fluorescence compared to nonfunctionalized and surface-fouled polyethylene. These results demonstrate the successful utilization of catechol-based materials for functionalizing polyolefin surfaces.

Dataset Information

Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer.

Publications

Synthesis and Characterization of Syndiotactic Polystyrene-Polyethylene Block Copolymer.

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