Hydroxyl end-capped telechelic polymers with poly(methyl methacrylate)-block-poly(n-butyl acrylate) (PMMA-b-PBA) backbones have been prepared via atom transfer radical polymerisation (ATRP) together with a nucleophilic substitution reaction. A hydroxyl-functionalised PMMA macroinitiator (HO-PMMA-Br) was prepared via ATRP at the optimised reaction temperature (60 8C) using 2-hydroxyethyl 2-bromoisobutyrate as the initiator. The high functionality of the bromo end group in the macroinitiator was confirmed by both 1H NMR technique and a chain-extension reaction. Electrospray ionisation mass spectrometer proved to be a valuable tool for characterising PMMAs with a bromo end group (PMMA-Br), which provided signals corresponding to the intact polymers although multiply charged polymer chains were observed. The well-defined block copolymers HO-PMMA-b-PBA-Br were obtained by the ATRP of n-butyl acrylate using HOPMMA-Br as a macroinitiator in a one-pot reaction at 100 8C. The kinetics as well as the dependence of the Mn;SEC and PDIs of the obtained block copolymers on the conversions of n-butyl acrylate in the chain-extension reaction suggested negligible radical termination during the reaction, demonstrating that the well-defined HO-PMMA-b-PBA-Br with a high functionality of bromo end group were obtained. The nucleophilic substitution reaction of a monohydroxyl-functionalised block copolymer HO-PMMA-b-PBA-Br with 5-amino-1-pentanol in dimethyl sulfoxide at room temperature was verified with 1H and 13C NMR techniques, which resulted in a series of telechelic polymers HOPMMA-b-PBA-OH with a functionality of hydroxyl groups up to 1.7 according to the gradient polymer elution chromatography.

采用高温溶液缩聚方法合成了一系列含带推-拉电子结构偶氨基团与介晶基团的聚酯型高分子，并利用红外光谱、元素分析、TG-DTA、热台偏光显微镜及x射线衍射等手段对其结构、相变行为、热分解过程及结晶性能进行了研究。结果表明，所合成的合偶氨基团与介晶基团的聚酯型高分子均为结晶性无规共聚性，其玻璃化转变温度随聚合物中偶氮含量的增加而升高，而熔融温度则随聚合物中偶氟含量的增加而降低；此外，研究结果还表明，各聚合物均具有很好的热稳定性，且含偶氨基团的聚酯型高分子的热分解过程是分3个阶段进行的。

High-throughput experimentation (HTE) was successfully applied in atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) for the rapid screening and optimization of different reaction conditions. A library of 108 different reactions was designed for this purpose, which used four different initiators [ethyl 2-bromoisobutyrate, methyl 2-bromopropionate, (1-bromoethyl)benzene, and p-toluenesulfonyl chloride], five metal salts (CuBr, CuCl, CuSCN, FeBr2, and FeCl2), and nine ligands (2,2-bipyridine and its derivatives). The optimal reaction conditions for Cu(I) halide, CuSCN, and Fe(II) halide-mediated ATRP systems with 2,2-bipyridine and its 4,4-dialkyl-substituted derivatives as ligands were determined. Cu(I)-mediated systems were better controlled than Fe(II)-mediated ones under the examined conditions. A bipyridine-type ligand with a critical length of the substituted alkyl group (i.e., 4,4-dihexyl 2,2-bipyridine) exhibited the best performance in Cu(I)-mediated systems, and p-toluenesulfonyl chloride and ethyl 2-bromoisobutyrate could effectively initiate Cu(I)-mediated ATRP of MMA, resulting in polymers with low polydispersities in most cases. Besides, Cu(I) halide-mediated ATRP with 4,5-dimethyl 2,2-bipyridine as the ligand and p-toluenesulfonyl chloride as the initiator proved to be better controlled than those with 4,4-dimethyl 2,2-bipyridine as the ligand, and polymers with much lower polydispersities were obtained in the former cases. This successful HTE example opens up a way to significantly accelerate the development of new catalytic systems for ATRP and to improve the understanding of structure–property relationships of the reaction systems.

The controlled atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) catalyzed by iron halide/N-(n-hexyl)-2-pyridylmethanimine (NHPMI) is described. The ethyl 2-bromoisobutyrate (EBIB)-initiated ATRP with [MMA]0/[EBIB]0/[iron halide]0/[NHPMI]0 150/1/1/2 was better controlled in 2-butanone than in p-xylene at 90°C. Initially added iron(III) halide improved the controllability of the reactions in terms of molecular weight control. The p-toluenesulfonyl chloride (TsC1)-initiated ATRP were uncontrolled with [MMA]0/[TsC1]0/[iron halide]0/[NHPMI]0 150/1/1/2 in 2-butanone at 90°C. In contrast to the EBIB-initiated system, the initially added iron(III) halide greatly decreased the controllability of the TsC1-initiated ATRP. The ration of iron halide to NHPMI significantly influenced the controllability of both EBIB and TsC1-initiated ATRP systems. The ATRP with [MMA]0/[initiator]0/[iron halide]0/[NHPMI]0 150/1//1/2 provided polymers with PDIs 1.57, whereas those with [iron halide]0/[NHPMI]0 1 resulted in polymers with PDIs as low as 1.35. Moreover, polymers with PDIs of approximately 1.25 were obtained after their precipitation from acidified methanol. The high functionality of the halide end group in the obtained polymer was confirmed by both 1H NMR and a chain-extenstion reaction. Cyclic voltammetry was utilized to explain the differing catalytic behaviors of the in situ-formed complexes by iron halide and NHPMI with different molar ratios.

The first monomode microwave-assisted atom transfer radical polymerization (ATRP) is reported. The ATRP of methyl methacrylate was successfully performed with microwave heating, which was well controlled and provided almost the same results as experiments with conventional heating, demonstrating the absence of any "microwave effect" in ATRP (in contrast to several literature reports). Furthermore, we found that the main advantage of the microwave-assisted reactions over conventional reactions, i.e., a significant increase of reaction rates, only had its limited application in ATRP, even in very slow ATRP systems with high targeted molecular weights.

The combination of iron(II) bromide with one equivalent of N-(n-hexyl)-2-pyridylmethanimine is shown to be an efficient catalyst for the well-controlled atom transfer radical polymerisation of methyl methacrylate.

9-(Guanidinomethyl)anthracene derivatives with a bromo (6) or a vinyl group (10) at the 10-position have been prepared starting from 9-bromoanthracene (1). They show 1:1 complexation with carboxylic acids or carboxylates with K-values of 1.2-1.4×105 M−1 in deuteriomethanol. Copolymerization of 9-vinylanthracene, 9-(guanidinomethyl)-10-vinylanthracene hydrochloride (10), and the 1:1 complex of 10 and ammonium benzoate with ethyleneglycol dimethacrylate (EDMA) gave the polymers in 77-92% yield. © 2001 Elsevier Science Ltd. All rights reserved.

The kinetics of CuBr-mediated homogeneous atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) using 2-hydroxyethyl-2-bromoisobutyrate (HEBIB) as initiator and N-(nhexyl) pyridylmethanimine (NHPMI) as ligand was investigated. The experimental results showed that initially added Cu(II) can have strong effects on the kinetics of the ATRP depending on the [Cu(II)]0/[Cu(I)]0 ratio. When e10% Cu(II) relative to Cu(I) was added at the beginning of the polymerization, the kinetics can be well described by Fischer's equation (ln([M]0/[M]) µ t2/3).9 The obtained reaction orders for initiator, Cu(I) and Cu(II), are quite close to or the same as those in Fischer's equation, verifying the applicability of Fischer's equation in ATRP systems. On the other hand, when [Cu(II)]0/[Cu(I)]0 g 0.1, the kinetics can be well interpreted by Matyjaszewski's equation (ln([M]0/[M]) µ t).8 The polymerization rate shows almost first order with respect to the concentrations of initiator and Cu(I) and inverse first order with respect to the concentration of Cu(II), suggesting that the "self-regulation" and radical termination becomes unimportant for the ATRP process when enough Cu(II) is added at the beginning of the reaction. This result is of great potential importance for better control of ATRP systems. Besides, the equilibrium constant Keq and termination constant kt of the ATRP system at 90°C were determined to be 7.2 10-8 and 8.9 107 M-1 s-1, respectively.

The synthesis of anthracene end-capped poly(methyl methacrylate)s via atom transfer radical polymerization (ATRP) and the kinetic analyses thereof are reported. Methyl methacrylate was polymerized in toluene at 90°C (or 60°C) via ATRP using 9-anthracenemethyl-2-bromoisobutyrate as the initiator and CuBr/N-(n-hexyl)pyridylmethanimine as the catalyst. Anthracene end-capped polymers with predetermined molecular weights and low polydispersities (PDI < 1.3) were obtained and characterized by 1H NMR and UV-vis. The initiator and Cu(I) concentrations, initially added Cu(II) concentration, and reaction temperature of the ATRP system have a decisive effect on the kinetics of the reaction. When the initiator and Cu(I) concentrations or the reaction temperature are relatively high, or the initially added Cu(II) concentration is relatively low, and consequently the radical concentration in the system is relatively high, the kinetics of the polymerization fits Fischer's equation (ln([M]0/[M]) µ t2/3). On the other hand, Matyjaszewski's equation (ln([M]0/[M]) µ t) can be fitted quite well when the initiator and Cu(I) concentrations or the reaction temperature are so low or the initially added Cu(II) concentration becomes so high that radical termination is negligible. This kinetic transition is of great importance for better understanding the mechanism of ATRP. The equilibrium and termination constants (Keq and kt) for the studied ATRP system at 90℃ are 9.1 10-8 and 1.3 108 M-1 s-1, respectively. The experimental evidence for Fischer's theoretically derived threshold Cu(II) concentration for the kinetic transition, i.e., [Cu(II)]0,t) (3Keq[RX]0[Cu(I)]0kt/kp)1/2, is provided.