New Chemical Modification of Polymers with Pendant Chloromethyl Groups Using 1,8-Diazabicyclo-[5.4.0]-7-undecene
New Chemical Modification of Polymers with Pendant Chloromethyl Groups Using 1,8-Diazabicyclo-[5.4.0]-7-undecene
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使用 1,8-二氮杂双环-[5.4.0]-7-十一碳烯对带有氯甲基侧基的聚合物进行新的化学改性
DOI：
10.1295/polymj.28.155
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发表时间：
1996
期刊：
影响因子：
2.8
通讯作者：
T. Nishikubo
中科院分区：
文献类型：
--
作者：
Atsushi Kameyama;Misao Suzuki;Kazuhiro Ozaki;T. Nishikubo
使用 1,8-二氮杂双环-[5.4.0]-7-十一碳烯 (DBU) 作为有机碱，聚[(对氯甲基)苯乙烯] (PCMS) 与苯甲酸和乙酸的酯化反应即使在 30°C，在非质子极性溶剂如 N,N-二甲基甲酰胺 (DMF)、N-甲基-2-吡咯烷酮和二甲基亚砜（DMSO）。聚（2-氯乙基乙烯基醚）（PCEVE）和聚（环氧氯丙烷）（PECH）与苯甲酸在 DBU 存在下在 DMF 中反应也得到带有侧苯甲酸酯部分的相应聚合物。然而，PCEVE和PECH的反应活性低于PCMS。此外，PCMS 与 N-保护的氨基酸（例如 Boc-L-丙氨酸、Cbz-L-丙氨酸和 Bz-DL-丙氨酸）使用 DBU 在 DMSO 中的高转化率反应，得到具有侧挂氨基酸残基的相应聚合物。从这些结果可以得出结论，DBU 是在温和反应条件下聚合物中侧氯甲基与羧酸发生酯化反应的极其有用的有机碱。
The esterification reaction of poly[(p-chloromethyl)styrene] (PCMS) with benzoic acid and acetic acid proceeded very smoothly to give the corresponding polymers with pendant ester residues using 1,8-diazabicyclo-[5.4.0]-7-undecene (DBU) as an organic base even at 30°C in aprotic polar solvents such as N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone, and dimethyl suloxide (DMSO). The reaction of poly(2-chloroethyl vinyl ether) (PCEVE) and poly(epichlorohydrin) (PECH) with benzoic acid in the presence of DBU in DMF also gave corresponding polymers with pendant benzoate moieties. However, the reactivities of PCEVE and PECH were lower than that of PCMS. Furthermore, the reaction of PCMS with N-protected amino acids such as Boc-L-alanine, Cbz-L-alanine, and Bz-DL-alanine afford corresponding polymers with pendant amino acid residues in high conversions using DBU in DMSO. From these results, it was concluded that DBU is the extremely useful organic base for the esterfication reaction of the pendant chloromethyl groups in the polymers with carboxylic acids under mild reaction conditions.