Bio-Based Functional Styrene Monomers Derived from Naturally Occurring Ferulic Acid for Poly(vinylcatechol) and Poly(vinylguaiacol) via Controlled Radical Polymerization
Bio-Based Functional Styrene Monomers Derived from Naturally Occurring Ferulic Acid for Poly(vinylcatechol) and Poly(vinylguaiacol) via Controlled Radical Polymerization
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DOI：
10.1021/acs.macromol.7b00970
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发表时间：
2017-05
期刊：
影响因子：
5.5
通讯作者：
Hisaaki Takeshima;K. Satoh;M. Kamigaito
中科院分区：
文献类型：
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作者：
Hisaaki Takeshima;K. Satoh;M. Kamigaito
以天然存在的阿魏酸为原料，通过脱羧得到天然存在的乙烯基酚类化合物4-乙烯基愈创木酚（4VG: 4-羟基-3-甲氧基苯乙烯），用于合成具有良好定义的具有酚功能的生物基聚乙烯基愈创木酚和聚乙烯基儿茶酚。通过4VG的一步化学转化，合成了一系列乙酰基（Ac4VG）、叔丁基二甲基硅基（TBDMS4VG）、三乙基硅基（TBDMS4VG）保护的4VG衍生物以及双（三乙基硅基）保护的乙烯基儿茶酚（TES2VC），产率高达90%。这些受保护的生物基酚醛苯乙烯单体在适当的可逆加成-裂解链转移（RAFT）剂或烷氧胺（有或没有自由基引发剂，如4,4 ' -偶氮（异丁腈）（AIBN））存在下成功地进行了可控自由基聚合，得到了分子量可控的聚合物。双分子结合反应即使在较高的单体密度下也被抑制。
A naturally occurring vinylphenolic compound, 4-vinylguaiacol (4VG: 4-hydroxy-3-methoxystyrene), which is derived from naturally occurring ferulic acid via decarboxylation, was used for the synthesis of well-defined bio-based poly(vinylguaiacol) and poly(vinylcatechol) with phenolic functions. Through one-step chemical conversions of 4VG, a series of 4VG derivatives protected with acetyl (Ac4VG), tert-butyldimethylsilyl (TBDMS4VG), or triethylsilyl (TBDMS4VG) groups as well as bis(triethylsilyl)-protected vinyl catechol (TES2VC) were synthesized with high yields (>90%). The controlled radical polymerization of these protected bio-based phenolic styrene monomers successfully proceeded in the presence of appropriate reversible addition–fragmentation chain transfer (RAFT) agents or alkoxyamines with or without radical initiators such as 4,4′-azobis(isobutyronitrile) (AIBN) to result in polymers with controlled molecular weights. Bimolecular combination reactions were suppressed even at the high monomer conve...