Mısır Murat, Savaskan Yılmaz Sevil, Bilgin Ahmet
Faculty of Engineering and Architecture, Department of Chemical Engineering, Kırşehir Ahi Evran University, Kırşehir 40100, Turkey.
Faculty of Sciences, Department of Chemistry, Karadeniz Technical University, University Avenue, Trabzon 61080, Turkey.
Polymers (Basel). 2023 Sep 18;15(18):3813. doi: 10.3390/polym15183813.
Syntheses of novel bifunctional poly(methyl methacrylate) (PMMA)-, poly(styrene) (PS)-, and (poly -caprolactone) (PCL)-based atom transfer radical polymerization (ATRP) macroinitiators derived from -xylene-bis(1-hydroxy-3-thia-propanoloxy) core were carried out to obtain ABA-type block copolymers. Firstly, a novel bifunctional ATRP initiator, 1,4-phenylenebis(methylene-thioethane-2,1-diyl)bis(2-bromo-2-methylpropanoat) (PXTBR), synthesized the reaction of -xylene-bis(1-hydroxy-3-thia-propane) (PXTOH) with α-bromoisobutryl bromide. The PMMA and PS macroinitiators were prepared by ATRP of methyl methacrylate (MMA) and styrene (S) as monomers using (PXTBR) as the initiator and copper(I) bromide/,,,,-pentamethyldiethylenetriamine (CuBr/PMDETA) as a catalyst system. Secondly, di(α-bromoester) end-functionalized PCL-based ATRP macronitiator (PXTPCLBr) was prepared by esterification of hydroxyl end groups of PCL-diol (PXTPCLOH) synthesized by Sn(Oct)-catalyzed ring opening polymerization (ROP) of -CL in bulk using (PXTOH) as initiator. Finally, ABA-type block copolymers, PXT(PS--PMMA--PS), PXT(PMMA--PS--PMMA), PXT(PS--PCL--PS), and PXT(PMMA--PCL--PMMA), were synthesized by ATRP of MMA and S as monomers using PMMA-, PS-, and PCL-based macroinitiators in the presence of CuBr/PMDETA as the catalyst system in toluene or ,-dimethylformamide (DMF) at different temperatures. In addition, the extraction abilities of PCL and PS were investigated under liquid-liquid phase conditions using heavy metal picrates (Ag, Cd, Cu, Hg, Pb, and Zn) as substrates and measuring with UV-Vis the amounts of picrate in the 1,2-dichloroethane phase before and after treatment with the polymers. The extraction affinity of PXTPCL and PXTPS for Hg was found to be highest in the liquid-liquid phase extraction experiments. Characterizations of the molecular structures for synthesized novel initiators, macroinitiators, and the block copolymers were made by spectroscopic (FT-IR, ESI-MS, H NMR, C NMR), DSC, TGA, chromatographic (GPC), and morphologic SEM.
合成了基于对二甲苯双（1-羟基-3-硫代丙醇氧基）核的新型双功能聚甲基丙烯酸甲酯（PMMA）、聚苯乙烯（PS）和聚己内酯（PCL）基原子转移自由基聚合（ATRP）大分子引发剂，以获得ABA型嵌段共聚物。首先，通过对二甲苯双（1-羟基-3-硫代丙烷）（PXTOH）与α-溴异丁酰溴反应合成了一种新型双功能ATRP引发剂1,4-亚苯基双（亚甲基硫代乙烷-2,1-二基）双（2-溴-2-甲基丙酸酯）（PXTBR）。以（PXTBR）为引发剂、溴化亚铜/五甲基二亚乙基三胺（CuBr/PMDETA）为催化体系，通过甲基丙烯酸甲酯（MMA）和苯乙烯（S）的ATRP制备了PMMA和PS大分子引发剂。其次，通过以（PXTOH）为引发剂，在本体中用辛酸亚锡（Sn(Oct)）催化ε-己内酯（ε-CL）的开环聚合（ROP）合成的PCL二醇（PXTPCLOH）的羟基端基酯化，制备了双（α-溴酯）端基功能化的基于PCL的ATRP大分子引发剂（PXTPCLBr）。最后，以PMMA、PS和PCL基大分子引发剂为原料，在CuBr/PMDETA作为催化体系存在下，于甲苯或N,N-二甲基甲酰胺（DMF）中不同温度下，通过MMA和S的ATRP合成了ABA型嵌段共聚物PXT(PS-b-PMMA-b-PS)、PXT(PMMA-b-PS-b-PMMA)、PXT(PS-b-PCL-b-PS)和PXT(PMMA-b-PCL-b-PMMA)。此外，在液-液相条件下，以重金属苦味酸盐（Ag、Cd、Cu、Hg、Pb和Zn）为底物，用紫外-可见光谱法测量聚合物处理前后1,2-二氯乙烷相中苦味酸盐的量，研究了PCL和PS的萃取能力。在液-液萃取实验中发现PXTPCL和PXTPS对Hg的萃取亲和力最高。通过光谱（FT-IR、ESI-MS、1H NMR、13C NMR）、DSC、TGA、色谱（GPC）和形态学SEM对合成的新型引发剂、大分子引发剂和嵌段共聚物的分子结构进行了表征。
