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Characterization of a commercial hyperbranched aliphatic polyester based on 2,2-bis(methylol)propionic acid

机译:基于2,2-双(羟甲基)丙酸的市售超支化脂族聚酯的表征

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摘要

A fourth generation hyperbranched polyester polyol based on bis-MPA and a PP50 core molecule (Boltorn H40) as well as its fractions obtained by preparative SEC were characterized with respect to composition, molar mass, and structure using NMR, SEC-MALS, ESI-MS, and DSC techniques. The content of dendritic units and the degree of branching (DB) are significantly lower than expected for a random polymerization, thus indicating that the hydroxyl groups in the linear repeat units are less reactive than those in terminal repeat units. The main side reaction in the synthesis of Boltorn H40 is deactivation of the bis-MPA carboxyl groups leading to structures without a core molecule. This side reaction influences mainly M-n, and to a lesser degree the M-w value of Boltorn H40. Furthermore, some of the hydroxyl groups react to ether groups. Etherification as a side reaction is of minor importance since the content of ether groups is below 1%. The obtained results indicate that despite deactivation of carboxyl groups of bis-MPA, the use of the PP50 core molecule in the polycondensation of bis-MPA permits control of the molar mass and polydispersity index, whereas the DB is not influenced. The Mw of Boltorn H40 is comparable to, and M. is significantly lower than, the theoretical molar mass of dendritic poly(bis-MPA) with a PP50 core molecule. [References: 47]
机译:使用NMR,SEC-MALS,ESI-NMR对基于bis-MPA和PP50核心分子(Boltorn H40)的第四代超支化聚酯多元醇以及通过制备SEC获得的馏分进行了组成,摩尔质量和结构的表征MS和DSC技术。树突单元的含量和支化度(DB)明显低于无规聚合的预期,因此表明线性重复单元中的羟基反应性低于末端重复单元中的羟基。 Boltorn H40合成中的主要副反应是bis-MPA羧基的失活,导致没有核心分子的结构。该副反应主要影响M-n,而对Boltorn H40的M-w值影响较小。此外,一些羟基与醚基反应。由于醚基的含量低于1%,因此醚化作为副反应的重要性不高。所得结果表明,尽管双-MPA的羧基失活,但在双-MPA的缩聚中使用PP50核心分子仍可控制摩尔质量和多分散指数,而DB不受影响。 Boltorn H40的Mw与具有PP50核心分子的树枝状聚(bis-MPA)的理论摩尔质量相当,并且M.显着低于其理论摩尔质量。 [参考:47]

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