Statistical Copolymers of n-Butyl Vinyl Ether and 2-Chloroethyl Vinyl Ether via Metallocene-Mediated Cationic Polymerization. A Scaffold for the Synthesis of Graft Copolymers.

Zouganelis Zouganelis,Pitsikalis Pitsikalis,Goulas Goulas,Choinopoulos Choinopoulos

doi:10.3390/polym11091510

Zouganelis Zouganelis, Pitsikalis Pitsikalis + Show 2 more

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https://doi.org/10.3390/polym11091510

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Journal: Polymers	Publication Date: Sep 16, 2019
Citations: 7	License type: CC BY 4.0

Affiliation: National and Kapodistrian University of Athens

Abstract

The cationic statistical copolymerization of n-butyl (be) and 2-chloroethyl vinyl ether (CEVE), is efficiently conducted using bis(η5-cyclopentadienyl)dimethyl zirconium (Cp2ZrMe2) in combination with tetrakis(pentafluorophenyl)borate dimethylanilinum salt [B(C6F5)4]–[Me2NHPh]+, as an initiation system. The reactivity ratios are calculated using both linear graphical and non-linear methods. Structural parameters of the copolymers are obtained by calculating the dyad sequence fractions and the mean sequence length, which are derived using the monomer reactivity ratios. The glass transition temperatures (Tg) of the copolymers are measured by Differential Scanning Calorimetry (DSC), and the results are compared with predictions based on several theoretical models. The statistical copolymers are further employed as scaffolds for the synthesis of graft copolymers having poly(vinyl ether)s as a backbone and either poly(ε-caprolactone) (PCL) or poly(l-lactide) (PLLA) as side chains. Both the grafting “onto” and the grafting “from” methodologies are employed. The reaction sequence is monitored by Size Exclusion Chromatography (SEC), NMR and IR spectroscopies. The advantages and limitations of each approach are thoroughly examined.

Highlights

Poly(vinyl ethers) (PVEs) are considered one of the most valuable classes of polymeric materials, due both to their academic interest and their industrial applications. These include their use as adhesives, surface coatings, lubricants, greases, elastomers, melting compounds, fibers and films [1]. Their molecular weight, the nature of their side alkyl group, the nature of the initiator used for their polymerization, their stereospecifity and their crystallinity directly affect their properties
PVEs are produced as viscous sticky liquids, rubbery or brittle solids or even as waxy materials when they contain long alkyl groups [2]
The cationic copolymerization of butyl vinyl ether (BVE) with chloroethyl vinyl ether (CEVE) was conducted in toluene solutions at 0 ◦ C

Summary

Introduction

Poly(vinyl ethers) (PVEs) are considered one of the most valuable classes of polymeric materials, due both to their academic interest and their industrial applications These include their use as adhesives, surface coatings, lubricants, greases, elastomers, melting compounds, fibers and films [1]. Their molecular weight, the nature of their side alkyl group, the nature of the initiator used for their polymerization, their stereospecifity and their crystallinity directly affect their properties. Poly(2-chloroethyl vinyl ether) (PCEVE) can be employed as an X-Ray-beam resist since its chlorine substituents on the alkoxy side chains improve sensitivity and resolution. PCEVE is hydrophobic, elastomeric and can be employed as an intermediate for the synthesis of more complicated macromolecular structures [3]

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