2,2,2-三氟乙基α-氟丙烯酸酯的热和光RAFT聚合<a href="#fn1" title="提供电子补充信息（ESI）。参见DOI：10.1039 / c8py00571k">†</a>,Polymer Chemistry

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2,2,2-三氟乙基α-氟丙烯酸酯的热和光RAFT聚合 †
Polymer Chemistry ( IF 4.1 ) Pub Date : 2018-05-29 00:00:00 , DOI: 10.1039/c8py00571k
Qizhi Yang _{1,

2,

3,

4,

5} , Marc Guerre _{1,

2,

3,

4,

5} , Vincent Ladmiral _{1,

2,

3,

4,

5} , Bruno Ameduri _{1,

2,

3,

4,

5}

Affiliation

在热条件和光辐射下研究了2,2,2-三氟乙基α-氟丙烯酸酯（FATRIFE）的RAFT聚合。4种不同链转移剂的性能（3,5-二甲基-1 H-吡唑-1-碳二硫酸酯（CTA ₁），4-氰基-4-（2-苯基乙硫基硫代羰基羰基）亚硫基戊酸（CTA ₂），三苄基三硫代碳酸酯（CTA）₃），和在热条件下比较了2-（苯基碳硫代硫基硫代）丙酸乙酯（CTA ₄））。CTA ₂，得到具有相对低的分散度聚合的相对良好的控制（表观摩尔质量中号_N，SEC〜37.8公斤摩尔^-1与PMMA，Đ<1.10）。观察到伪一级聚合动力学和摩尔质量相对于单体转化率的线性增加。使用CTA ₂作为链转移剂和白色LED灯（14 W×2），在光照射下进一步研究了FATRIFE的RAFT聚合。在没有外源自由基源或催化剂的情况下，在室温下观察到受控的聚合。摩尔质量（最多25.3 kg mol ^-1）随单体转化率和低分散度（Đ）线性增加<1.10）已成功获得。使用光开/关实验也观察到聚合的时间控制。通过photoRAFT合成的基于聚（FATRIFE）的macroCTA还扩展了1,1,1,3,3,3-六氟丙烷-2-基-2-氟丙烯酸酯和叔丁基-2-三氟甲基丙烯酸酯/ FATRIFE。

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Thermal and photo-RAFT polymerization of 2,2,2-trifluoroethyl α-fluoroacrylate†

The RAFT polymerization of 2,2,2-trifluoroethyl α-fluoroacrylate (FATRIFE) was investigated under thermal conditions and light irradiation. The performances of 4 different chain transfer agents (3,5-dimethyl-1H-pyrazole-1-carbodithioate (CTA₁), 4-cyano-4-(2-phenylethanesulfanylthiocarbonyl)sulfanylpentanoic acid (CTA₂), dibenzyl trithiocarbonate (CTA₃), and ethyl 2-(phenylcarbonothioylthio) propionate (CTA₄)) were compared under thermal conditions. CTA₂ afforded relatively good control of the polymerization with relatively low dispersities (apparent molar mass M_n,SEC ∼ 37.8 kg mol⁻¹vs. PMMA, Đ < 1.10). Pseudo-first-order polymerization kinetics and a linear increase of the molar masses versus monomer conversions were observed. The RAFT polymerization of FATRIFE was further explored under photoirradiation using CTA₂ as the chain transfer agent and white LED lamps (14 W × 2). In the absence of exogenous radical sources or catalysts, controlled polymerization was observed at room temperature. A linear increase of molar masses (up to 25.3 kg mol⁻¹) with monomer conversions and low dispersities (Đ < 1.10) were successfully obtained. Temporal control of the polymerization was also observed using light ON/OFF experiments. Poly(FATRIFE) based macroCTA synthesized by photoRAFT was also extended with 1,1,1,3,3,3-hexafluoropropan-2-yl 2-fluoroacrylate and tert-butyl-2-trifluoromethacrylate/FATRIFE.

更新日期：2018-05-29

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