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以铁氰化钾为氧化剂,通过N-咔唑二硫代甲酸钠的水相氧化制备了高纯度的中间体二硫化双(N-咔唑硫代甲酰)(DTCD),DTCD以晶体的形式从水中析出,提纯简单,性质稳定.通过DTCD与偶氮二异丁腈(AIBN)或偶氮二氰基戊酸(ACVA)的反应合成了2种性能优异的叔丁腈酯基RAFT试剂,N-咔唑二硫代甲酸异丁腈酯(CYCBD)和N-咔唑二硫代甲酸氰基戊酸(CVCBD),新合成工艺的副反应和杂质被大量减少,最终产物的收率可达80%以上.以CYCBD和CVCBD为可逆加成断裂链转移(RAFT)试剂,研究了它们对甲基丙烯酸甲酯(MMA)RAFT聚合的控制能力,结果表明CYCBD和CVCBD是性能优异的RAFT试剂,可以很好地用于制备结构明确、分子量分布窄的链末端咔唑标记的聚甲基丙烯酸甲酯(CPMMA),由它们所制得的CPMMA的PDI小于1.2.研究结果还表明CYCBD和CVCBD及由其合成的CPMMA在四氢呋喃(THF)溶液中具有显著的荧光特性,CPMMA在358nm处有很强的荧光发射峰,而且,在浓度范围为0.1～20μmol/L的THF溶液中,CPMMA的荧光发射强度与其浓度具有良好的线性关系.通过CYCBD和CVCBD可以方便地制备结构明确且具荧光标识的功能聚合物。
Using potassium ferricyanide as oxidant, bis (N-carbazolethiocarbamyl) disulfide (DTCD), an intermediate of high purity, was prepared by aqueous phase oxidation of sodium N-carbazole dithiocarboxylate. It is simple and stable to be purified from water, and two kinds of excellent TBTS RAFT reagents were synthesized by the reaction of DTCD with azobisisobutyronitrile (AIBN) or azobiscyanovaleric acid (ACVA) N-carbazodithioic acid isobutyronitrile (CYCBD) and N-carbazole dithiocarbonic acid cyanovaleric acid (CVCBD), the side effects of the new synthesis process and impurities are greatly reduced, the yield of the final product can be Up to more than 80% .Their control ability of RAFT on CYCBD and CVCBD for MMA RAFT polymerization was studied.The results showed that CYCBD and CVCBD are excellent RAFT agents , Which can be well used to prepare chain-ended carbazole-labeled polymethylmethacrylate (CPMMA) with well-defined and narrow molecular weight distribution and CPMMA prepared from them has a PDI of less than 1.2. The results also show that CYCBD and CVCBD And CPMMA synthesized from it have significant fluorescence characteristics in tetrahydrofuran (THF) solution. CPMMA has a strong fluorescence at 358 nm , And the fluorescence intensity of CPMMA had a good linear relationship with the concentration in the range of 0.1 ~ 20μmol / L THF solution.It can be easily prepared by CYCBD and CVCBD that the structure has clear and fluorescent labeling function polymer.