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首页> 外文期刊>Journal of Polymer Science, Part A. Polymer Chemistry >Radical copolymerization of novel trifluorovinyl ethers with ethyl vinyl ether and vinyl acetate: Estimating reactivity ratios and understanding reactivity behavior of the propagating radical
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Radical copolymerization of novel trifluorovinyl ethers with ethyl vinyl ether and vinyl acetate: Estimating reactivity ratios and understanding reactivity behavior of the propagating radical

机译：新型三氟乙烯基醚与乙基乙烯基醚和乙酸乙烯酯的自由基共聚：估计反应比并了解增长的自由基的反应性

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摘要

Two novel trifluorovinyl ether (TFVE) monomers were copolymerized with either ethyl vinyl ether (EVE) or vinyl acetate (VAc) in a redox-initiated aqueous emulsion: 1-(2-phenoxyethoxy)-1,2,2-trifluoroethene (Ph-TFVE) and 1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene (Et-TFVE). Previous studies demonstrated a propensity for radical hydrogen abstraction from the oligoether pendant group during the homopolymerization of Et-TFVE with continued propagation of the resulting radical, thereby providing the rationale to investigate the copolymerization of our new TFVEs with EVE or VAc. Reactivity ratios were estimated using the error-in-variables model from a series of bulk free radical copolymerizations of Ph-TFVE with EVE or VAc. The reactivity ratios were r(Ph-TFVE) = 0.25 +/- 0.07, r(EVE) = 0.016 +/- 0.04; r(Ph-TFVE) = 0.034 +/- 0.04, r(VAc) = 0.89 +/- 0.08. Partial hydrolysis of polymers containing VAc to vinyl alcohol (VA) resulted in two terpolymers: poly(Ph-TFVE-co-VAc-co-VA) and poly(Et-TFVE-co-VAc-co-VA), respectively. We investigated the possibility of hydrogen abstraction from VAc during polymerization by comparing the molar mass before and after hydrolysis. Abstraction from VAc was not apparent during polymerization; however, abstraction from the oligoether pendant group of Et-TFVE was again evident and was more significant for those copolymers having a greater fraction of Et-TFVE in the monomer feed. (C) 2000 John Wiley & Sons, Inc. [References: 13]
机译：在氧化还原引发的水乳液中，将两种新型三氟乙烯基醚（TFVE）单体与乙基乙烯基醚（EVE）或乙酸乙烯酯（VAc）共聚：1-（2-苯氧基乙氧基）-1,2,2-三氟乙烯（Ph- TFVE）和1- [2-（2-乙氧基乙氧基）乙氧基] -1,2,2-三氟乙烯（Et-TFVE）。先前的研究表明，在Et-TFVE的均聚过程中，低聚醚侧基的自由基氢的夺取趋势以及生成的自由基的持续传播，从而为研究新的TFVE与EVE或VAc的共聚提供了理论依据。使用变量误差模型，根据Ph-TFVE与EVE或VAc的一系列本体自由基共聚反应，估算反应活性比。反应性比率为r（Ph-TFVE）＝ 0.25 +/- 0.07，r（EVE）＝ 0.016 +/- 0.04; r（EVE）＝ 0.016 +/- 0.04。 r（Ph-TFVE）= 0.034 +/- 0.04，r（VAc）= 0.89 +/- 0.08。含VAc的聚合物部分水解为乙烯醇（VA）分别得到两种三元共聚物：聚（Ph-TFVE-co-VAc-co-VA）和聚（Et-TFVE-co-VAc-co-VA）。通过比较水解前后的摩尔质量，我们研究了聚合过程中VAc析氢的可能性。在聚合过程中，从VAc提取没有明显作用。然而，从Et-TFVE的寡醚侧基中再次提取是明显的，并且对于在单体进料中具有更大Et-TFVE分数的那些共聚物而言更为重要。 （C）2000 John Wiley＆Sons，Inc. [参考：13]

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