Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have re...Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.展开更多
基金by the National Natural Science Foundation of China(No.21774090)National Key R&D Program of China(No.2018YFB1105700)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Due to the poor solubility of aromatic polyesters in comm on orga nic solve nts,trifluoroacetic acid is usually used as a co-solve nt to increase their solubility for characterizations.However,only few studies have reported the side reactions induced by it.We present here the application of in situ 1H-NMR techniques to explore its effect on the hydroxyl end-groups,which are usually used for the molecular weight determination of polyesters by end-group estimation method.Using bis(2-hydroxyethyl)terephthalate(BHET)as model compound,quantitative NMR results show the peak integration of hydroxyethyl end-groups decreased with time via a pseudo-first-order kinetics in d-trifluoroacetic acid/d-chloroform mixture solvent(1:10,V:V).This is due to the esterification of hydroxyethyl groups with trifluoroacetic acid,revealed by the H-^(13)C gradient-enhanced heteronuclear multiple bond correlation(gHMBC)spectrum.The mixtures of dimethyl terephthalate and BHET with different molar ratios were used to represent poly(ethylene terephthalate)(PET)with different degrees of polymerization,and the effect of trifluoroacetic acid on the estimation of hydroxyethyl groups and subsequent molecular weight determination of polyesters was studied.Our results show that if a relative error of 5%is allowed,the NMR measurements must be finished within 1.3 h of solution preparation at 25℃ in the mixture solve nt.The results were confirmed in PET sample,while in poly(ethyle ne adipate),the obtained esterifaction con stant is faster that those in aromatic system.The results can be applied to other polymer systems with alcohol functionalized groups,and used as a guideline for the characterization of polyesters and polyethers by end-group estimation method.
