END-FUNCTIONALIZED POLYMERS BY LIVING CATIONIC POLYMERIZATION .1. MONO FUNCTIONAL AND BIFUNCTIONAL POLYVINYL ETHERS) WITH TERMINAL MALONATE OR CARBOXYL GROUPS
END-FUNCTIONALIZED POLYMERS BY LIVING CATIONIC POLYMERIZATION .1. MONO FUNCTIONAL AND BIFUNCTIONAL POLYVINYL ETHERS) WITH TERMINAL MALONATE OR CARBOXYL GROUPS
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DOI：
10.1021/ma00167a001
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发表时间：
1987-01-01
期刊：
影响因子：
5.5
通讯作者：
HIGASHIMURA, T
中科院分区：
文献类型：
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作者：
SAWAMOTO, M;ENOKI, T;HIGASHIMURA, T
末端单和双官能单分散聚以碘化氢/碘引发体系[CH_3CH_（-3）]为引发剂，通过乙烯基醚的活性阳离子聚合，合成了丙二酸酯、丙二酸酯钠盐或相应的羧酸作为末端官能团X的（乙烯基醚）I ~ III（OCH2CH2X）-（CH2CH（OR））n-OCH3（I），H-（CH2CH（OR））n-X（II），CH3CH（OCH2CH2X）-（CH2CH（OR））n-X（III）（X= CH（COOC2H5）2，CH（COONa）2，CH2COOH; R= CH3，CH2CH（CH3）2）]。主链聚合物为亲水性聚（甲基乙烯基醚）和亲脂性聚（异丁基乙烯基醚）。采用两种方法合成单官能丙二酸酯封端聚合物：（1）（I型）在碘存在下，由乙烯基醚-碘化氢加成物CH 3CHIOCH 2CH（COOC 2 H5）2（官能引发剂）引发乙烯基醚的活性聚合;（2）（II型）由碘化氢/碘引发体系得到的活性聚乙烯基醚用丙二酸阴离子~ CH（COOC 2 H5）2封端。两种方法的组合得到III型遥爪丙二酸酯聚合物。I-III的丙二酸酯末端可以通过碱催化水解然后脱羧转化为相应的羧酸。根据NMR分析和/或电导滴定，这些单官能和双官能聚合物的末端官能度分别接近1和2。
Terminally mono- and bifunctional monodisperse poly (vinyl ethers) I—III, carrying malonic ester, its sodium salt, or the corresponding carboxylic acid as terminal function X, were synthesized by living cationic polymerization of vinyl ethers by the hydrogen iodide/iodine initiating system [CH3CH-(OCH2CH2X)-(CH2CH (OR))„-OCH3 (I), H-(CH2CH (OR))„-X (II), CH3CH (OCH2CH2X)-(CH2CH (OR))„-X (III)(X= CH (COOC2H5) 2, CH (COONa) 2, CH2COOH; R= CH3, CH2CH (CH3) 2)]. The backbone polymers were hydrophilic poly (methyl vinyl ether) and lipophilic poly (isobutyl vinyl ether). Two methods were employed for the synthesis of the monofunctional malonate-capped polymers:(1)(for type I) living polymerization of vinyl ethers initiated by a vinyl ether-hydrogeniodide adduct CH3CHIOCH2CH2CH (COOC2H5) 2 (a functional initiator) in the presence of iodine; and (2)(for type II) end-capping ofliving poly (vinyl ether), obtained by the hydrogen iodide/iodineinitiating system, with the malonate anion~ CH (COOC2H5) 2. Combination of the two methods gave telechelic malonate polymers of type III. The malonic ester terminals of I—III could be transformed into the corresponding carboxylic acids by base-catalyzed hydrolysis followed by decarboxylation. The end functionalities of these mono- and bifunctional polymers were close to 1 and 2, respectively, according to NMR analysis and/or conductometric titration.