Morales-Cerrada Roberto, Ladmiral Vincent, Gayet Florence, Fliedel Christophe, Poli Rinaldo, Améduri Bruno
ICGM, Univ. Montpellier, CNRS, ENSCM, Montpellier, France.
CNRS, LCC (Laboratoire de Chimie de Coordination), Université de Toulouse, UPS, INPT, 205 route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France.
Polymers (Basel). 2020 Feb 8;12(2):384. doi: 10.3390/polym12020384.
The use of [Mn(R)(CO)] (R = CF, CHF, CHCF COCFCH) to initiate the radical polymerization of vinylidene fluoride (FC=CH, VDF) and the radical alternating copolymerization of vinyl acetate (CH=CHOOCCH, VAc) with -butyl 2-(trifluoromethyl)acrylate (MAF-TBE) by generating primary R radicals is presented. Three different initiating methods with [Mn(CF)(CO)] (thermal at ca. 100 °C, visible light and UV irradiations) are described and compared. Fair (60%) to satisfactory (74%) polyvinylidene fluoride (PVDF) yields were obtained from the visible light and UV activations, respectively. Molar masses of PVDF reaching 53,000 g·mol were produced from the visible light initiation after 4 h. However, the use of [Mn(CHF)(CO)] and [Mn(CHCF)(CO)] as radical initiators produced PVDF in a very low yield (0 to 7%) by both thermal and photochemical initiations, while [Mn(COCFCH)(CO)] led to the formation of PVDF in a moderate yield (7% to 23%). Nevertheless, complexes [Mn(CHCF)(CO)] and [Mn(COCHF)(CO)] efficiently initiated the alternating VAc/MAF-TBE copolymerization. All synthesized polymers were characterized by H and F NMR spectroscopy, which proves the formation of the expected PVDF or poly(VAc--MAF-TBE) and showing the chaining defects and the end-groups in the case of PVDF. The kinetics of VDF homopolymerization showed a linear ln[M]/[M] versus time relationship, but a decrease of molar masses vs. VDF conversion was noted in all cases, which shows the absence of control. These PVDFs were rather thermally stable in air (up to 410 °C), especially for those having the highest molar masses. The melting points ranged from 164 to 175 °C while the degree of crystallinity varied from 44% to 53%.
介绍了使用[Mn(R)(CO)]（R = CF、CHF、CHCF₂COCF₂CH₃）通过产生初级R自由基引发偏二氟乙烯（FC=CH₂，VDF）的自由基聚合以及乙酸乙烯酯（CH₂=CHOOCCH₃，VAc）与2-（三氟甲基）丙烯酸丁酯（MAF-TBE）的自由基交替共聚。描述并比较了使用[Mn(CF₃)(CO)]的三种不同引发方法（约100℃热引发、可见光和紫外线照射）。分别通过可见光和紫外线活化获得了相当（60%）到令人满意（74%）的聚偏二氟乙烯（PVDF）产率。4小时后，通过可见光引发制备的PVDF摩尔质量达到53,000 g·mol⁻¹。然而，使用[Mn(CHF₂)(CO)]和[Mn(CHCF₂)(CO)]作为自由基引发剂，通过热引发和光化学引发制备PVDF的产率都非常低（0%至7%），而[Mn(COCF₂CH₃)(CO)]导致PVDF以中等产率（7%至23%）形成。尽管如此，配合物[Mn(CHCF₂)(CO)]和[Mn(COCHF₂)(CO)]有效地引发了VAc/MAF-TBE交替共聚。所有合成的聚合物都通过¹H和¹⁹F NMR光谱进行了表征，这证明了预期的PVDF或聚（VAc-MAF-TBE）的形成，并显示了PVDF的链缺陷和端基。VDF均聚的动力学显示ln[M]₀/[M]与时间呈线性关系，但在所有情况下都注意到摩尔质量随VDF转化率降低，这表明缺乏控制。这些PVDF在空气中相当热稳定（高达410℃），特别是对于那些具有最高摩尔质量的PVDF。熔点范围为164至175℃，而结晶度从44%变化到53%。
