Living cationic polymerization of vinyl ethers with a tricyclodecane or tricyclodecene unit: Synthesis of new poly(vinyl ether)s with high glass‐transition temperature
Living cationic polymerization of vinyl ethers with a tricyclodecane or tricyclodecene unit: Synthesis of new poly(vinyl ether)s with high glass‐transition temperature
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具有三环癸烷或三环癸烯单元的乙烯基醚的活性阳离子聚合：合成具有高玻璃化转变温度的新型聚（乙烯基醚）
DOI：
10.1002/pola.20224
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
T. Kodaira
中科院分区：
文献类型：
--
作者：
Takeshi Namikoshi;T. Hashimoto;T. Kodaira
在可阳离子聚合的单体中，乙烯醚类是乙烯基阳离子聚合的代表之一。乙烯基醚阳离子聚合的活性特性提供了各种定义明确的聚合物，其垂坠和末端具有官能团。虽然这种功能化的聚乙烯醇醚在特定用途上是很有前途的功能聚合物，但几乎没有完全由聚乙烯醇醚骨架组成的商品聚合物（即一般用途的结构聚合物材料）的例子。烷基乙烯醚的聚合物在室温下呈橡胶状，烷基为线性链。聚（烷基乙烯基醚）s的玻璃化转变温度（Tg）示例如下：12烷基：甲基，34℃；乙基，42 C；正丁基，55℃；n-octyl;就其玻璃化转变温度低而言，这种聚（烷基乙烯基醚）具有用作橡胶或弹性体的潜力。最近，日本商业化开发了端羟基远旋聚乙基乙烯醚，用于合成具有聚乙基乙烯醚软段的新型聚氨酯。这些热塑性聚氨酯弹性体是具有软段和硬段交替的分段嵌段共聚物，其中在软嵌段基体中形成的聚氨酯硬嵌段域作为物理交联点，赋予聚合物橡胶弹性。另一种基于聚乙烯醚的热塑性弹性体的候选材料是aba型嵌段共聚物，其中a是高Tg的硬聚合物段，B是低Tg的软聚合物段。为了制备这种完全由聚乙烯醚骨架组成的新型弹性体聚合物，需要对高Tg聚乙烯醚的合成进行控制。我们之前获得高Tg聚乙烯醚的方法包括在聚乙烯醚的侧链上合成氨基甲酸酯基团。然而，聚（环己基乙烯基醚）的玻璃化转变温度（Tg; 50 C15）比聚（正己基乙烯基醚）（Tg; 77 C12）高得多。这一事实表明，在聚乙烯醚的垂链中引入多环单元可能会使其Tg升高到足以适用于塑料材料的温度。在本研究中，三种新型乙烯基醚具有三环烷烃和烯烃单元，8-乙烯基氧基三环[5.2]。[1.02, 6]癸烷(1)，8-和9-乙烯基氧三环[5.2]。[1.02, 6]-癸-3-烯(2)和8-乙烯氧基甲基三环[5.2]。以1.02,6]-癸烷(3)为单体，合成了具有刚性三环单元的新型聚乙烯醚（方案1）。特别关注的是生者
Among cationically polymerizable monomers, the class of vinyl ether is one of the representatives in cationic vinyl polymerization. 1–3 The living character of the cationic polymerization of vinyl ethers provided a variety of well-defined polymers with functional groups in their pendants and terminals. 4–11 Although such functionalized poly (vinyl ether) s are promising functional polymers for particular purposes, there are almost no examples of commodity polymers (ie, structural polymeric materials for general purpose use) consisting totally of poly (vinyl ether) backbones. Polymers of alkyl vinyl ethers are rubbery at room temperature when the alkyls are linear chains. Examples of glass-transition temperature (Tg) of poly (alkyl vinyl ether) s are as follows; 12 alkyl: methyl, 34 C; ethyl, 42 C; n-butyl, 55 C; n-octyl; 80 C. In terms of their low glass-transition temperature, such poly (alkyl vinyl ether) s have potential to be used as rubber or elastomer. Recently, hydroxyl-terminated telechelic poly (ethyl vinyl ether) s were commercially developed in Japan, 13 which are applicable for the synthesis of new polyurethanes with poly (vinyl ether) soft segments. 13 These thermoplastic polyurethane elastomers are a segmented block copolymer having alternating soft and hard segments, in which the urethane hard block domains formed in the soft block matrix serve as physical crosslinking points to impart rubber elasticity to the polymers. Another candidate for thermoplastic elastomers based on poly (vinyl ether) s is a ABA-type block copolymer, where the A is a hard polymer segment with high Tg and the B is a soft polymer segment with low Tg. To prepare such new elastomeric polymers consisting totally of poly (vinyl ether) backbones, the controlled synthesis of poly (vinyl ether) s with high Tg is necessary. Our previous approach to obtain poly (vinyl ether) s with high Tg involved the synthesis of poly (vinyl ether) s with urethane groups in their side chains. 14However, poly (cyclohexyl vinyl ether) exhibits much higher glass-transition temperature (Tg; 50 C15) than poly (n-hexyl vinyl ether)(Tg; 77 C12). This fact suggests that introduction of polycyclic units into pendant chains of poly (vinyl ether) s may increase their Tg up to temperatures high enough to apply for plastic materials. In the present study, three types of new vinyl ethers with a tricyclic alkane and alkene unit, 8-vinyloxytricyclo-[5.2. 1.02, 6] decane (1), 8-and 9-vinyloxytricyclo [5.2. 1.02, 6]-dec-3-ene (2), and 8-vinyloxymethyltricyclo [5.2. 1.02, 6]-decane (3), were employed as monomers for the synthesis of new poly (vinyl ether) s with rigid tricyclic units (Scheme 1). Particular attention was focused on the living