Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

窄分布聚丙烯酸-g-聚甲基丙烯酸酯接枝共聚物的合成

利用合成的一种新型原子转移自由基聚合大分子引发剂和从主干接枝的方法制备了窄分布的两亲性接枝共聚物聚丙烯酸-g-聚甲基丙烯酸酯, 并对其结构进行表征. 产物主链和侧链的分子量可分别通过调整单体与引发剂的投料比和反应时间进行控制, 结构规整, 侧链单体适用范围广. 该合成方法不仅推动了接枝共聚物合成研究的进展, 其产物更为两亲性接枝共聚物自组装行为的研究提供了很好的研究对象.     

用含偶氮基的聚苯乙烯大分子引发剂合成两亲性嵌段共聚物

采用含偶氮基的聚苯乙烯预聚物（ＰＳ ＡＣＰＣ）作为引发剂，合成了苯乙烯（Ｓｔ）分别与甲基丙烯酸（ＭＡＡ）、甲基丙烯酸（β 羟丙酯）（ＨＰＭＡ）的嵌段共聚物，考察了ＰＳ ＡＣＰＣ引发第二单体的聚合反应行为，以及影响第二单体转化率和均聚物含量、共聚物组成的因素．用溶解性、凝胶渗透色谱（ＧＰＣ）、红外光谱（ＩＲ）、核磁共振（ＮＭＲ）、动态接触角（ＤＣＡ）等表征了嵌段共聚物．     

Synthesis of PDMAEMA-PCL-PDMAEMA triblock copolymers

The synthesis of ABA triblock copolymers of the type PDMAEMA-PCL-PDMAEMA was achieved by atom transfer radical polymerization (ATRP) of DMAEMA using difunctional polycaprolactone (PCL) as macroinitiator. First, ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) was carried out in the presence of 1,2-diaminoethane/tin (II) octanoate. Dihydroxy PCL thus obtained was end-functionalized in a quantitative manner using 2-bromoisobutyryl bromide. The resulting Br-PCL-Br was used as macroinitiator in the ATRP of DMAEMA leading to triblock copolymers with PCL as the central block and PDMAEMA sequences of different lengths. NMR and SEC analyses confirmed the formation of ABA triblocks.     

Dendritic Macroinitiator for the Ring—Opening Polymerization of γ—Benzyl L—Glutamate N—Carboxyanhydride

Much effort has been dedicated to the molecular design and synthesis of model proteins to define protein folding interactions and to develop protein-based materials. Among them, the ring-opening polymerization of -amino acid-N-carboxyanhy- drides (NCAs) has drawn much attention because the resulting artificial polypeptides have wide applications in biotechnology, biomineralization and diagnostics1, 2. It is well known that dendrimers are hyperbranched macromolecules possessing a very high co…     

Synthesis and Characterization of Amphiphific Block Copolymer Containing PVP and Poly（5-benzyloxytrimethylene carbonate）

Amphiphilic copolymer of 5-benzyloxytrimethylene carbonate （BTMC） with poly （vinyl pyrrolidone） （PVP） was successfully synthesized using immobilized porcine pancreas lipase （IPPL） or SnOct2 as catalyst. Hydroxyl terminated PVP, synthesized with 2-mercaptoethanol as a chain transfer reagent, was employed as a rnacroinitiator. The resulting copolymers were characterized by GPC, ^1H NMR and IR. Increasing the BTMC/PVP-OH feed ratio （[B]/[P]） resulted in the increase of Mn of corresponding copolymers and the decrease of Mw/Mn. Immobilized enzyme has comparable catalytic activity to SnOct2 for the copolymerization.     

Poly(ascorbyl acrylate)s: Synthesis and evaluation of their redox polymerization ability in the presence of hydrogen peroxide

In this work, a strategy for chemical synthesis of ascorbic acid functionalized polyacrylates (PAAA) was accomplished in a two‐step process, first a reversible addition fragmentation chain‐transfer (RAFT) polymerization on a benzyl‐protected ascorbyl acrylate monomer, followed by a deprotection (debenzylation) reaction. The polymers were characterized by ¹H NMR, ¹³C NMR and gel permeation chromatograph. The polymerization ability of redox pair including PAAA and H₂O₂ were conducted through the measurement of 2‐hydroxyethyl acrylate (HEA) conversion against time via real‐time FT‐NIR. It was found that PAAA in the presence of H₂O₂, independent on itself chain length, exhibited much faster polymerization than small molecule ascorbic acid (smAA) as reductant at identical condition. Interestingly, when the concentration of ascorbate repeating unit was over some critical value, the polymerization kinetics of HEA could be tunable by simply adjusting the initial molar ratio of reductant to oxidant and environmental pH. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Block copolymers derived from polyisobutylene oligomers

The synthesis of polyvalent functionalized polyisobutylene (PIB) oligomers containing multiple polar groups via radical polymerization is described. Polymerizations from PIB macroinitiators via alkylborane intermediates can form block copolymers but the polar block is consistently larger than the PIB block and unless a hydrophobic monomer is used, the products are insoluble in alkanes. Block copolymer products from ATRP macroinitiators are formed with more control over the degree of polymerization of a polar block from a 1000 Da PIB starting material but are still alkane insoluble because the degree of polymerization of the polar block was consistently equal to or greater than the degree of polymerization of the PIB block. RAFT polymerization using 5 mol % of azoisobutyronitrile relative to a PIB macroinitiator however was successful in producing acceptable yields of alkane soluble block copolymers using a 1000 Da PIB starting material and monomers like methyl methacrylacrylate, ethyl methacrylate, N,N‐dimethylacrylamide, and N‐isopropylacrylamide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1860–1867     

Combining atom‐transfer radical polymerization and ring‐opening polymerization through bifunctional initiators derived from hydroxy benzyl alcohol—Preparation and characterization of initiators,macroinitiators, and block copolymers

A simple, one‐step procedure has been developed for the preparation of bifunctional initiators capable of polymerizing monomers suitable for atom‐transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP). These bifunctional initiators were employed for making narrow disperse poly(styrene) macroinitiators, which were subsequently used for the ROP of various lactides to yield poly(styrene‐block‐lactide) copolymers. Thermogravimetric analysis (TGA) of these block copolymers are interesting in that it shows a two‐step degradation curve with the first step corresponding to the degradation of poly(lactide) segment and the second step associated with the poly(styrene) segment of the block copolymer. This nature of the block copolymer makes it possible to estimate the block copolymer content by TGA in addition to the ¹H NMR spectroscopic analysis. Thus, this study for the first time highlights the possibility of making porous materials by thermal means which are otherwise obtained by base hydrolysis. The bifunctional initiators were prepared by the esterification of 3‐hydroxy, 4‐hydroxy, and 3,5‐dihydroxy benzyl alcohols with α‐bromoisobutyryl bromide and 2‐bromobutyryl bromide. A mixture of products was obtained, which were purified by column chromatography. The esterified benzyl alcohols were employed in the polymerization of styrene under copper (Cu)‐catalyzed ATRP conditions to yield macroinitiators with low polydispersity. These macroinitiators were subsequently used in the ROP of L ‐, DL ‐, and mixture of lactides. The formation of block copolymers was confirmed by gel permeation chromatography (GPC), spectroscopic and thermal characterizations. The molecular weight of the block copolymers was always higher than the macroinitiator, and the GPC chromatogram was symmetrical indicating the uniform initiation of ROP by the macroinitiators. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 102–116, 2008     

Facile and versatile synthesis of rod‐coil poly(3‐hexylthiophene)‐based block copolymers by nitroxide‐mediated radical polymerization

A well‐defined and monofunctional poly(3‐hexylthiophene)‐based (P3HT) macroinitiator has been obtained through a clean, simple, and an efficient multistep synthesis process. The macroinitiator is obtained via intermolecular radical 1,2‐addition onto an ω‐acrylate‐terminated P3HT macromonomer. In a second step, well‐defined rod‐coil block copolymers were obtained by nitroxide‐mediated radical polymerization (NMRP) using the so‐called Blocbuilder^®. The polymerization was found to be controlled with various monomers such as styrene, isoprene, 4‐vinylpyridine, or methyl acrylate. This process constitutes a very promising way to obtain versatile and clean materials for organic electronics. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012