络合剂TTPO的合成及催化剂溶解度对原子转移自由基聚合的影响
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摘要
本论文由以下三个部分组成:三(1-四氢吡咯代)氧磷(TTPO)和三(4-吗啉代)氧磷(TMPO)的合成,表征以及其作为铁系络合剂参与MMA的原子转移自由基聚合;原子吸收测定铜含量的方法定量研究铜催化体系在单MMA和溶剂DMF中的溶解含量,考察催化剂的溶解性对MMA的原子转移自由基聚合的影响;N-氯代丁二酰亚胺(NCS),N-溴代丁二酰亚胺(NBS)分别作为引发转移终止剂和原子转移自由基聚合引发剂的比较研究。
一、TTPO由原料三氯氧磷和四氢吡咯合成制得,产物结构由元素分析和核磁测试确证。以FeCl_2·4H_02O/TTPO为催化剂,分别以2-溴异丁酸乙酯(EBiB)和二氯化苄为引发剂,动力学研究MMA的原子转移自由基聚合。结果显示TTPO可以作为原子转移自由基聚合的铁系络合剂,是一个典型的原子转移自由基聚合体系,扩链反应进一步证明了体系活性可控的特征。与其他的铁系络合剂三苯基磷,结构相似的六甲基磷酰三胺相比较,磷氧类络合剂聚合速率较三苯基磷慢,但分子量分布窄,聚合物的分子量与理论计算值相符。三(1-四氢吡咯代)氧磷也可以应用于反向原子转移自由基聚合,体系AIBN/FeCl_3·6H_2O/TTPO/MMA有更好的可控性,分子量分布在1.2左右。TMPO由三氯氧磷和吗啉合成制得,产物结构由元素分析和核磁分析确证。TMPO作为原子转移自由基聚合的络合剂活性不好。
二、用单齿配体三乙胺(TEA),二齿配体联吡啶(bipy),三齿配体(PMDETA,MA5-DETA,MA4-DETA,MA3-DETA)为络合剂,分别与Cu(Ⅰ)、Cu(Ⅱ)络合,由原子吸收测定铜含量的方法定量测定不同催化体系在单体MMA中的溶解含量,动力学研究不同催化体系的MMA的原子转移自由基聚合,考察催化剂的溶解性能对原子转移自由基聚合的影响。结果显示,溶剂DMF提高了催化剂的溶解量,但催化剂并不是完全溶解在单体与溶剂中;络合剂的取代基的种类及个数对催化体系的溶解性能有很大的影响。络合剂是原子转移自由基聚合的必要组成成分,在没有络合剂存在的条件下,氯化亚铜和引发剂不能催化引发MMA溶液聚合,溶剂DMF不起到络合剂的作用;对于活性聚合体系(CuCl/bipy,
The thesis is composed of three parts: Synthesis and characterization of new ligands Tri (1-pyrrolidino) phosphine oxide (TTPO) and Tri (4-morpholino) phosphine oxide (TMPO), which were also used in the ATRP of MMA complexed by Fe(Ⅱ); Atomic Abstract Measurement for the quantitive determination of soluble Copper Complexes in MMA and the relationship between solubility of the catalyst system and the ATRP; The comparison of NCS and NBS used as initiator for ATRP and iniferter reagent.
1.Tri (1-pyrrolidino) phosphine oxide (TTPO) was synthesized by phosphorus oxychloride and pyrrolidine. The resulted product was confirmed by element analysis and ~1H NMR spectra. The ATRP of MMA catalyzed by FeCl_2·4H_2O/TTPO with EBiB and DCT as initiator were carried out respectively. The kinetic plot showed that TTPO could be used as the ligand of ATRP and it turned out to be a typical ATRP system. The living controlled characteristic was further confirmed by chain extension. Compared to other ligand, such asPhP_3 and HMPA, the polymerization of MMA with HMPA and TTPO as the ligand gave predetermined polymers with relatively lower polydispersity. TTPO could also be used as iron catalyzed ligand in the RATRP of MMA, producing polymers with lower polydispersity (PDI≈1.2). Tri (4-morpholino) phosphine oxide (TMPO) was synthesized by phosphorus oxychloride and morpholine. Unfortunately TMPO used as the ligand of ATRP was not able to lead to living polymerization.
2.Several ligands such as monodentate nitrogen (TEA), bidentate ligand (bipy), tridentate ligands (PMDETA, MA_5-DETA, MA_4-DETA, MA_3-DETA) complexed by CuCl were employed in the ATRP of MMA in DMF. Atomic Abstract Measurement was carried out to determine the solubility of the catalyst system quantitively. It was found that the solvent DMF could improve the solubility of the catalyst system but the catalyst system was not completely soluble in the monomer. What’s more, the
一、TTPO由原料三氯氧磷和四氢吡咯合成制得,产物结构由元素分析和核磁测试确证。以FeCl_2·4H_02O/TTPO为催化剂,分别以2-溴异丁酸乙酯(EBiB)和二氯化苄为引发剂,动力学研究MMA的原子转移自由基聚合。结果显示TTPO可以作为原子转移自由基聚合的铁系络合剂,是一个典型的原子转移自由基聚合体系,扩链反应进一步证明了体系活性可控的特征。与其他的铁系络合剂三苯基磷,结构相似的六甲基磷酰三胺相比较,磷氧类络合剂聚合速率较三苯基磷慢,但分子量分布窄,聚合物的分子量与理论计算值相符。三(1-四氢吡咯代)氧磷也可以应用于反向原子转移自由基聚合,体系AIBN/FeCl_3·6H_2O/TTPO/MMA有更好的可控性,分子量分布在1.2左右。TMPO由三氯氧磷和吗啉合成制得,产物结构由元素分析和核磁分析确证。TMPO作为原子转移自由基聚合的络合剂活性不好。
二、用单齿配体三乙胺(TEA),二齿配体联吡啶(bipy),三齿配体(PMDETA,MA5-DETA,MA4-DETA,MA3-DETA)为络合剂,分别与Cu(Ⅰ)、Cu(Ⅱ)络合,由原子吸收测定铜含量的方法定量测定不同催化体系在单体MMA中的溶解含量,动力学研究不同催化体系的MMA的原子转移自由基聚合,考察催化剂的溶解性能对原子转移自由基聚合的影响。结果显示,溶剂DMF提高了催化剂的溶解量,但催化剂并不是完全溶解在单体与溶剂中;络合剂的取代基的种类及个数对催化体系的溶解性能有很大的影响。络合剂是原子转移自由基聚合的必要组成成分,在没有络合剂存在的条件下,氯化亚铜和引发剂不能催化引发MMA溶液聚合,溶剂DMF不起到络合剂的作用;对于活性聚合体系(CuCl/bipy,
The thesis is composed of three parts: Synthesis and characterization of new ligands Tri (1-pyrrolidino) phosphine oxide (TTPO) and Tri (4-morpholino) phosphine oxide (TMPO), which were also used in the ATRP of MMA complexed by Fe(Ⅱ); Atomic Abstract Measurement for the quantitive determination of soluble Copper Complexes in MMA and the relationship between solubility of the catalyst system and the ATRP; The comparison of NCS and NBS used as initiator for ATRP and iniferter reagent.
1.Tri (1-pyrrolidino) phosphine oxide (TTPO) was synthesized by phosphorus oxychloride and pyrrolidine. The resulted product was confirmed by element analysis and ~1H NMR spectra. The ATRP of MMA catalyzed by FeCl_2·4H_2O/TTPO with EBiB and DCT as initiator were carried out respectively. The kinetic plot showed that TTPO could be used as the ligand of ATRP and it turned out to be a typical ATRP system. The living controlled characteristic was further confirmed by chain extension. Compared to other ligand, such asPhP_3 and HMPA, the polymerization of MMA with HMPA and TTPO as the ligand gave predetermined polymers with relatively lower polydispersity. TTPO could also be used as iron catalyzed ligand in the RATRP of MMA, producing polymers with lower polydispersity (PDI≈1.2). Tri (4-morpholino) phosphine oxide (TMPO) was synthesized by phosphorus oxychloride and morpholine. Unfortunately TMPO used as the ligand of ATRP was not able to lead to living polymerization.
2.Several ligands such as monodentate nitrogen (TEA), bidentate ligand (bipy), tridentate ligands (PMDETA, MA_5-DETA, MA_4-DETA, MA_3-DETA) complexed by CuCl were employed in the ATRP of MMA in DMF. Atomic Abstract Measurement was carried out to determine the solubility of the catalyst system quantitively. It was found that the solvent DMF could improve the solubility of the catalyst system but the catalyst system was not completely soluble in the monomer. What’s more, the
引文
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