Unraveling the Spontaneous Zwitterionic Copolymerization Mechanism of Cyclic Imino Ethers and Acrylic Acid,Macromolecules

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Unraveling the Spontaneous Zwitterionic Copolymerization Mechanism of Cyclic Imino Ethers and Acrylic Acid
Macromolecules ( IF 5.1 ) Pub Date : 2018-01-08 00:00:00 , DOI: 10.1021/acs.macromol.7b02608
Jan Steinkoenig _{1,

2,

3} , Patrick A. J. M. de Jongh ₄ , David M. Haddleton _{4,

5} , Anja S. Goldmann _{1,

2,

3} , Christopher Barner-Kowollik _{1,

2,

3} , Kristian Kempe _{4,

5}

Affiliation

We report a high-resolution electrospray ionization mass spectrometric (HR ESI-MS) access route leading to in-depth insights into the spontaneous zwitterionic copolymerization mechanism between cyclic imino ethers (i.e., 2-methyl-2-oxazoline (MeOx), 2-ethyl-2-oxazoline (EtOx), or 2-ethyl-2-oxazine (EtOz)) with acrylic acid (AA), exploiting the characteristic species accumulating during the copolymerization as well as tandem mass spectrometry (MS/MS). We demonstrate preferences in α,ω-end group formation by screening various feed ratios of cyclic imino ethers and acrylic acid (e.g., MeOx:AA = 1:1; MeOx:AA = 2:1; and MeOx:AA = 1:2). Critically, a calibration curve—based on AA-MeOx-AA dimer—was established allowing for the semiquantitative determination of the end-group ratios with different feed ratios of acrylic acid. The formation of previously suggested alternating copolymers was confirmed by MS/MS experiments. Deviations from an ideal alternating composition were found to decrease from MeOx to EtOx to EtOz. The results of (semiquantitative) HR ESI-MS and MS/MS measurements suggest, for the first time presented in such precision, a polymerization mechanism for the spontaneous zwitterionic (alternating) copolymerization indicating optimal monomer ratios and pairings.

中文翻译：

揭示环状氨基醚与丙烯酸的自发性两性离子共聚机理

我们报告了高分辨率电喷雾电离质谱（HR ESI-MS）的访问途径，导致对环亚氨基醚（即2-甲基-2-恶唑啉（MeOx），2-乙基-2-恶唑啉（EtOx）或2-乙基-2-恶嗪（EtOz））与丙烯酸（AA），利用了在共聚以及串联质谱（MS / MS）过程中积累的特征性物质。通过筛选环状亚氨基醚和丙烯酸的各种进料比（例如MeOx：AA = 1：1; MeOx：AA = 2：1; MeOx：AA = 1：2），我们证明了在α，ω端基形成方面的偏好）。至关重要的是，建立了基于AA-MeOx-AA二聚体的校准曲线，从而可以半定量确定不同丙烯酸进料比例下的端基比例。通过MS / MS实验证实了先前提出的交替共聚物的形成。发现与理想的交替组成的偏差从MeOx到EtOx到EtOz减少。（半定量）HR ESI-MS和MS / MS测量结果首次以这种精确度表明，自发性两性离子（交替）共聚的聚合机理表明了最佳的单体比例和配对。

更新日期：2018-01-08

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