Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers
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模块化聚膦酸酯均聚物和共聚物的合成和表征

DOI:
10.1002/pol.20200066
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发表时间:
2020
影响因子:
3.4
通讯作者:
Gray, Gary M.
Gray, Gary M.
中科院分区:
化学3区
文献类型:
--
作者:
Totsch, Timothy R.;Stanford, Victoria L.;Klep, Oleksander;Burdette, Mary K.;Grant, Benjamin;Foulger, Stephen H.;Gray, Gary M.

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通过P(Ph)(NET2)2与二元醇(HOR‘OH=1,4-环己二甲醇、1,4-苯二甲醇、四甘醇或1,12-十二烷二醇)的缩聚反应,合成了通式为-[P(Ph)(X)OR’O]n-(X=S或Se)的线型多膦酸酯。P(Ph)(NEt2)2与二元醇按2:1:1摩尔比缩聚,然后与硫化物反应,合成了无规共聚物。Et2N[P(Ph)(X)OR‘O](x + 2)-[P(Ph)(X)OR’O](x + 3)-(X=S或Se)嵌段共聚物由Et2N[P(Ph)(X)OR‘O](x + 2)P(Ph)NEt2与HOR’O[P(Ph)(X)OR‘O](x + 3)H齐聚物缩聚而成。过量的P(Ph)(NET2)2与二元醇反应生成Et2N[P(Ph)(X)OR‘O](x + 2)P(Ph)NET2齐聚物,而HOR’O[P(Ph)(X)OR‘O](x + 3)H齐聚物通过P(Ph)(NET2)2与过量的二元醇反应生成。在每种情况下,多余的x是相同的,并确定平均块大小。用1H、13C{1H}和31P{1H}核磁共振谱、TGA、DSC和SEC对所有聚合物进行了表征。31P{1H}核磁共振谱表明,无规共聚物和嵌段共聚物具有预期的单体排列,对于嵌段共聚物,验证了嵌段尺寸。所有聚合物的热稳定性都高达~300°C,共聚物中单体的排列(嵌段排列与随机排列)会影响其降解温度和玻璃化温度分布。聚合物的重均相对分子质量高达3.8MWs× × 104Da。
Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2and a diol (HOR′OH = 1,4‐cyclohexanedimethanol, 1,4‐benzenedimethanol, tetraethylene glycol, or 1,12‐dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2)–[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using1H,13C{1H}, and31P{1H} NMR spectroscopy, TGA, DSC, and SEC.31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures andTgprofiles. The polymers have weight average MWs of up to 3.8 × 104Da.
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