Cationic Ring-Opening Polymerization of Five-Membered Cyclic Thiocarbonate Bearing an Adamantane Moiety via Selective Ring-Opening Direction
Cationic Ring-Opening Polymerization of Five-Membered Cyclic Thiocarbonate Bearing an Adamantane Moiety via Selective Ring-Opening Direction
复制标题
含金刚烷部分的五元环硫代碳酸酯选择性开环方向的阳离子开环聚合
DOI：
10.1021/ma012094i
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发表时间：
2002
期刊：
影响因子：
5.5
通讯作者：
T. Endo
中科院分区：
文献类型：
--
作者：
Hisamitsu Kameshima;N. Nemoto;F. Sanda;T. Endo
以1，2-金刚烷和硫代光气为原料，在吡啶存在下合成了一种新型的含金刚烷环的五元环硫代碳酸酯化合物4，6-二氧杂四环[6.3.1.1.3，1003，7]十三烷-5-酮（1）。在30 °C下，通过三乙基氧鎓四氟硼酸盐（Et 3 OBF 4）、三氟甲磺酸甲酯（TfOMe）、三氟甲磺酸（TfOH）和H2O与2摩尔%的三氟化硼醚合物（BF 3 OEt 2）在CH 2Cl 2中引发M2 O 1进行阳离子开环聚合，以通过硫代羰基异构化为具有选择性开环方向的羰基而得到聚硫代碳酸酯。用H2O/BF 3 OEt 2聚合得到的聚合物的数均分子量和多分散性分别为10600和1.44。所得聚合物的5%重量损失的温度为338 °C。在聚合过程中，MPEG 1膨胀高达14%。
A novel five-membered cyclic thiocarbonate bearing adamantane moiety, 4,6-dioxatetracyclo[6.3.1.1.3,1003,7]tridecane-5-thione (1), was synthesized from 1,2-adamantanediol and thiophosgene in the presence of pyridine. Monomer 1 underwent cationic ring-opening polymerization initiated by triethyloxonium tetrafluoroborate (Et3OBF4), methyl trifluoromethanesulfonate (TfOMe), trifluoromethanesulfonic acid (TfOH), and H2O with 2 mol % of boron trifluoride etherate (BF3OEt2) in CH2Cl2 at 30 °C to afford the polythiocarbonate by isomerization of the thiocarbonyl group into a carbonyl group with selective ring-opening direction. The number-average molecular weight and polydispersity of the polymer obtained by polymerization with H2O/BF3OEt2 were 10 600 and 1.44, respectively. The temperature with 5% weight loss of the obtained polymer was 338 °C. Monomer 1 expanded as large as 14% during the polymerization.