The chain propagations of Bisphenol A-aniline benzoxazine (defined as BA-a) polymerized by thermal induction and in the presence of various catalysts or curing agents during the curing process before gelation were investigated in this paper. DSC, gel time test and GPC were used to measure the curing behavior, number-average molecular weight (n), glass transition temperature (Tg), gel time (tgel) and curing conversion (α) of different benzoxazine systems. By comparing the experimental results (n and Tg) with the models of step polymerizations and chain polymerizations proposed by Flory et al., three kinds of chain propagations of benzoxazine were observed and confirmed. The step polymerization occurred in the thermal induction or in the presence of catalyst N,N-dibenzylaniline (tAm), and then the non-living chain polymerization and the living chain polymerization occurred, respectively, when indole (Id) and other additives such as phenol (tBp), acid (HA), imidazole (IMZ) etc. were added to benzoxazine as catalysts or curing agents. Moreover, the relationship between the chain propagation and curing kinetics of benzoxazine was also established. The chain propagation of benzoxazine systems involves step polymerization, non-living chain polymerization andliving chain polymerization, the conversion of the gel point (αgel) is almost equal to, less than and greater than the value of the conversion at which the polymerization rate reaches a maximum (αmax), respectively. The results may contribute to a better understanding of the polymerization mechanism of benzoxazine and provide new approaches to effective control of the polymerization kinetics and growth crosslink structures of benzoxazine.
Pengjia Yang,Wentao Zhong,Baiyu Jiang,Biao Zhang,Zhisheng Fu,Zhiqiang Fan
Propagation chains with 1,2 and 2,1 last-inserted monomer unit in 1-hexene polymerization with MgCl 2 -supported Ziegler-Natta catalysts were quench-labeled by thiophene-2-carbonyl chloride, and the two kinds of 2-thenoyl-labeled chain ends were determined by 1 H NMR analysis. The number of labeled chains was noticeably smaller than the number of dead chains formed by chain transfer with alkylaluminum cocatalyst, and grew with time more slowly than the latter, showing that side reactions between the quencher and Al-polymeryl moieties are negligible. The active sites with 2,1 last-inserted monomer were halted in dormant state, which lead to their gradual accumulation in the 30 s polymerization process. The catalyst containing phthalate type internal donor has higher percentage of dormant sites as compared with the catalyst containing diol ester. The combination of acyl chloride quench-labeling and 1 H NMR analysis forms a reliable and easily accessible method of tracing and characterizing active sites in transition metal catalyzed olefin polymerization.
Xiaoqiang Xue,Yangjing Chen,Kang Liang,Wenyan Huang,Hongjun Yang,Li Jiang,QiMin Jiang,Bibiao Jiang,Hongting Pu
The ring-forming behavior of polymers with an odd number of arms in highly dilute solutions has been studied using tri-arm polystyrene (PSt3) as a model through combining atom transfer radical polymerization (ATRP) and atom transfer radical coupling (ATRC) technologies. The star polymer, PSt3, with three arms and a central core was obtained by ATRP of styrene using a designed initiator with three active Br terminals and ester groups, followed by the Br terminal–Br terminal radical coupling of PSt3, which was implemented via intramolecular ATRC under high dilution conditions. A tadpole-shaped cyclic polymer (tadpole-PSt) was successfully prepared, proving that there no intermolecular side reactions that occur during the intramolecular ATRC of PSt3. Interestingly, the tadpole-PSt not only possesses a cyclic topology, but also contains a living chain, in contrast to other cyclic analogues that have been previously reported. Finally, the tadpole-PSt was used as a building block to construct a type of barbell polymer (barbell-PSt) by removing most of the solvent via vacuum distillation at the end of the intramolecular ATRC of PSt3. Size exclusion chromatography, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, 1H nuclear magnetic resonance spectroscopy and hydrolysis experiments proved that high-purity cyclic polymers (tadpole-PSt and barbell-PSt) were successfully prepared. The thermal properties of the cyclic and star polymers were analyzed using differential scanning calorimetry and thermogravimetric analysis. The results demonstrated that the formation of a cyclic topology makes a huge contribution to the increase in the glass transition temperature (Tg) and thermal stability of the polymer.
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