Thermoresponsive diblock copolymer micellar macro‐RAFT agent‐mediated dispersion RAFT polymerization and synthesis of temperature‐sensitive ABC triblock copolymer nanoparticles

The micellar macro‐RAFT agent‐mediated dispersion polymerization of styrene in the methanol/water mixture is performed and synthesis of temperature‐sensitive ABC triblock copolymer nanoparticles is investigated. The thermoresponsive diblock copolymer of poly(N,N‐dimethylacrylamide)‐block‐poly[N‐(4‐vinylbenzyl)‐N,N‐diethylamine] trithiocarbonate forms micelles in the polymerization solvent at the polymerization temperature and, therefore, the dispersion RAFT polymerization undergoes as similarly as seeded dispersion polymerization with accelerated polymerization rate. With the progress of the RAFT polymerization, the molecular weight of the synthesized triblock copolymer of poly(N,N‐dimethylacrylamide)‐block‐poly[N‐(4‐vinylbenzyl)‐N,N‐diethylamine]‐b‐polystyrene linearly increases with the monomer conversion, and the PDI values of the triblock copolymers are below 1.2. The dispersion RAFT polymerization affords the in situ synthesis of the triblock copolymer nanoparticles, and the mean diameter of the triblock copolymer nanoparticles increases with the polymerization degree of the polystyrene block. The triblock copolymer nanoparticles contain a central thermoresponsive poly [N‐(4‐vinylbenzyl)‐N,N‐diethylamine] block, and the soluble‐to‐insoluble ‐‐transition temperature is dependent on the methanol content in the methanol/water mixture. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2155–2165     

A novel high‐contrast ratio electrochromic material from spiro[cyclododecane‐1,9′‐fluorene]bicarbazole

A novel electroactive spirocyclododecylfluorene monomer named 2,7‐bis(carbazol‐9‐yl)‐9,9′‐spiro[cyclododecane‐1,9′‐fluorene] (SFC) was synthesized and electrochemically polymerized to give a very stable multi‐electrochromic polymer (poly‐SFC). Two separate oxidation processes were observed for both SFC monomer and poly‐SFC that carries two carbazole units. The polymeric film of poly‐SFC was coated onto ITO/glass surface, and it shows different colors (transparent, yellowish green, green, and dark green) upon stepwise oxidations. An electrochromic device based on poly‐SFC was assembled in the sandwich cell configuration of ITO/poly‐SFC//gel electrolyte//PEDOT/ITO. Poly‐SFC exhibits 90% of transparency at neutral state and a high contrast ratio (ΔT = 58% at 800 nm). This device constructed from it represents a response time of about 1 s, high coloration efficiency (1377 cm² C^–1) and retained its performance by 96.4% even after 1000 cycles. Exhibiting high transparency at neutral state, reversible redox behavior, resistance to overoxidation, and especially high contrast ratio at near IR region can make poly‐SFC be useful and promising candidate for electrochromic applications despite having a relatively slow response time. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Nanostructured hybrid polymer networks from in situ self‐assembly of RAFT‐synthesized POSS‐based block copolymers

A series of well‐defined hybrid block copolymers PMACyPOSS‐b‐PMMA and PMAiBuPOSS‐b‐PMMA exhibiting high POSS weight contents have been synthesized by RAFT polymerization and further studied as modifiers for epoxy thermosets based on diglycidyl ether of bisphenol A. The hybrid block copolymers self‐assembled within the epoxy precursors into micelles possessing an inorganic core and a PMMA corona. Thanks to the presence of the PMMA blocks that remain miscible until the end of the reaction, curing of the resulting blends afforded nanostructured hybrid organic/inorganic networks with well‐dispersed inorganic‐rich nanodomains with diameters on the order of 20 nm. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Photoinitiated precipitation polymerization in liquid CO2: Fast formation of crosslinked poly(acrylic acid‐co‐methoxy polyethylene glycol acrylate) microspheres

Photoinitiated precipitation polymerization of acrylic acid (AA) and methoxy polyethylene glycol acrylate (MPEGA) was carried out in liquid carbon dioxide using ethanol as cosolvent and trimethylol propane triacrylate (TMPTA) as crosslinker. Monodisperse crosslinked microspheres were obtained with size polydispersity index as low as 1.027. The particle yield rose sharply after irradiation and reached to 52% at 5 min, then gently increased to 65% at 60 min, suggesting that most of microspheres were produced in the first 5 min of irradiation. The particle number increased incessantly till very late stage of reaction, which could be attributed to the direct generation of stable nuclei from the fast crosslinking polymerization instead of oligomer aggregation. The effect of ethanol content, feeding ratio of monomers and crosslinker concentration on the morphologies, size, and dispersity of microspheres has been investigated. X‐ray photoelectron spectroscopy showed that the microspheres obtained by this procedure were covered with abundant carbon double bonds. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of poly(tert‐butyl methacrylate)‐graft‐poly(dimethylsiloxane) graft copolymers via reversible addition‐fragmentation chain transfer polymerization

Well‐defined poly(tert‐butyl methacrylate)‐graft‐poly (dimethylsiloxane) (PtBuMA‐g‐PDMS) graft copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) copolymerization of methacryloyl‐terminated poly (dimethylsiloxane) (PDMS‐MA) with tert‐butyl methacrylate (tBuMA) in ethyl acetate, using 2,2′‐azobis(isobutyronitrile) (AIBN) as the initiator and 2‐cyanoprop‐2‐yl dithiobenzoate as the RAFT agent. The RAFT statistical copolymerization of PDMS‐MA with tBuMA is shown to be azeotropic and the obtained PtBuMA‐g‐PDMS graft copolymers have homogeneously distributed branches because of the similar reactivity of monomers (r_tBuMA ≈ r_PDMS‐MA ≈ 1). By the RAFT block copolymerization of PDMS‐MA with tBuMA, moreover, narrow molecular weight distribution (M_w/M_n < 1.3) PtBuMA‐g‐PDMS graft copolymers with gradient or blocky branch spacing were synthesized. The graft copolymers exhibit the glass transitions corresponding to the PDMS and PtBuMA phase, respectively. However, the arrangement of monomer units in copolymer chains and the length of PtBuMA moieties have important effects on the thermal behavior of PtBuMA‐g‐PDMS graft copolymers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

RAFT‐based synthesis and the gelation property of telechelic polymers that can immobilize biomacromolecules

Telechelic polymers, macromolecules having two reactive end groups, can serve as building blocks for constructing polymers or polymeric materials that have complex architectures. Among the telechelic polymers, polymers bearing hydroxyl groups at two terminals have been used as components for preparation of functional materials. In the present study, RAFT polymerization of both N‐acryloylmorphorin and N‐succinimidyl acrylate by using a newly synthesized dithiobenzoate‐type chain transfer agent bearing hydroxyl groups at both terminals (HECPHD) was reported. After the acryloylation of the hydroxyl terminals of the obtained polymer, gelation was observed. Furthermore, the polymer could react with a protein via the conjugation of the succinimidyl esters‐containing polymers to the amino groups present on the protein surface. The results show that activated esters‐bearing polymers with hydroxyl groups at both terminals can be used as building blocks for constructing polymeric materials for an immobilization of biomacromolecules. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1356–1365     

RAFT polymerization of vinyl methacrylate and subsequent conjugation via enzymatic thiol‐ene chemistry

The polymerization of vinyl methacrylate (VMA) allows the synthesis of polymers with pendant double bonds. When this polymerization was undertaken in the presence of 2‐cyanopropyl dithiobenzoate as reversible addition–fragmentation chain transfer agent, it led almost exclusively to vinylester functional sidegroups, which were available for further reactions. The vinylester functionality could not be functionalized using common thiol‐ene catalysts, but could be activated using Candida antarctica lipase B (CAL‐B) (Novozyme 435). The reaction between PVMA and various thiols in N, N‐dimethyl formamide in the presence of CAL‐B led exclusively to the formation of the anti‐Markovnikov product. The rate of reaction between PVMA and 1‐butanethiol was monitored using ¹H NMR. The reaction was complete within 72 h. Similar results were obtained with other small‐sized thiols such as 2‐mercaptoethanol, 3‐mercaptopropionic acid, and 2‐(trimethylsilyl)ethanethiol, while more bulky thiols, such as secondary thiols, thiols with long alkyl chains, and sterically demanding thiols, such as mono(6‐deoxy‐6‐mercapto)‐β‐cyclodextrin, only led to lower conversions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Side chain crosslinking of aromatic polyethers for high temperature polymer electrolyte membrane fuel cell applications

Novel aromatic polymers bearing polar pyridine units in the main chain and side chain crosslinkable hydroxyl and propargyl groups have been successfully synthesized. The polymers have been investigated in terms of their critical properties related to their application in high temperature polymer electrolyte membrane fuel cells, such as doping ability, mechanical properties, and thermal stability. Crosslinked membranes were prepared by direct crosslinking of hydroxyl side chain groups with decafluorobiphenyl used for the first time as a crosslinking agent. However, further functionalization of hydroxyl groups to the propargyl derivative has also led to crosslinked polymers after thermal curing. Both types of crosslinked membranes exhibited higher glass transition temperatures as well as lower doping levels when doped in phosphoric acid compared with the non crosslinked analogs, confirming the formation of a successfully crosslinked network. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012