Synthesis,characterization, electrochromic properties,and electrochromic device application of a novel star polymer consisting of thiophene end‐capped poly(ε‐caprolactone) arms emanating from a hexafunctional cyclotriphosphazene core

Hexa‐armed and thiophene (Thi) end‐capped poly(ε‐caprolactone) star polymer (N₃P₃‐(PCL‐Thi)₆), containing cyclotriphosphazene core, was prepared in a four‐step reaction sequence. Ring‐opening polymerization (ROP) and “click chemistry” techniques were employed in the first and final steps, respectively. Hexa‐armed PCL star polymer (N₃P₃‐(PCL‐OH)₆) was successfully synthesized via ROP of ε‐caprolactone (ε‐CL) by using hekzakis(p‐(hydroxymethyl)phenoxy) cyclotriphosphazene as the multisite initiator and tin(II) 2‐ethylhexanoate (Sn(Oct₂)) as the catalyst in bulk at 115 °C. Further modifications of the N₃P₃‐(PCL‐OH)₆ were accomplished by derivatization of the hydroxyl‐functional chain ends. The obtained N₃P₃‐(PCL‐OH)₆ was then reacted with 2‐bromo‐2‐methylpropanoyl bromide, and this led to a star polymer with bromide end groups, N₃P₃‐(PCL‐Br)₆. In the third step, N₃P₃‐(PCL‐Br)₆ was azidified with sodium azide (NaN₃) in DMF affording N₃P₃‐(PCL‐N₃)₆. Conversion of the azide chain end groups into Thi was quantitatively accomplished via the “click reaction” between N₃P₃‐(PCL‐N₃)₆ and prop‐2‐yn‐1‐yl 3‐thienyl acetate in the final step. Subsequently, the star polymer with six Thi chain ends (N₃P₃‐(PCL‐Thi)₆) was employed in electrochemical copolymerization with both pyrrole and Thi. Electrochromic properties and electrochromic device application of N₃P₃‐(PCL‐Thi)₆/PThi were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3668–3682, 2010     

Supramolecular inclusion complexes of a star polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms with β‐cyclodextrin

A novel hexa‐armed and star‐shaped polymer containing cholesterol end‐capped poly(ε‐caprolactone) arms emanating from a phosphazene core (N₃P₃‐(PCL‐Chol)₆) was synthesized by a combination of ring‐opening polymerization and “click” chemistry techniques. For this purpose, the terminal ? OH groups of the synthesized precursor (N₃P₃‐(PCL‐OH)₆) were converted into –Chol through a series of reaction. Both N₃P₃‐(PCL‐OH)₆ and N₃P₃‐(PCL‐Chol)₆ were then employed in the preparation of supramolecular inclusion complexes (ICs) with β‐cyclodextrin (β‐CD). The latter formed ICs with β‐CD in higher yield. The host–guest stoichiometry (ε‐CL:β‐CD, mol:mol) in the ICs of N₃P₃‐(PCL‐Chol)₆ was found to be 1.2. The formation of supramolecular ICs of N₃P₃‐(PCL‐Chol)₆ with β‐CD was confirmed by using Fourier transform infrared (FTIR) and ¹H nuclear magnetic resonance (NMR) spectroscopic methods, wide‐angle X‐ray diffraction (WAXD), and thermal analysis techniques. WAXD data showed that the obtained ICs with N₃P₃‐(PCL‐Chol)₆ had a channel‐type crystalline structure, indicating the suppression of the original crystallization of N₃P₃‐(PCL‐Chol)₆ in β‐CD cavities. Moreover, the thermal stabilities of ICs were found to be higher than those of the free star polymer and β‐CD. Furthermore, the surface properties of N₃P₃‐(PCL‐Chol)₆ and its ICs with β‐CD were investigated by static contact angle measurements. The obtained results proved that the wettability of N₃P₃‐(PCL‐Chol)₆ successfully increased with the formation of its ICs with β‐CD. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3406–3420     

Synthesis,characterization, and fluorescence of pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer with pentaerythritol core

Novel and well‐defined pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymers were successfully achieved by combination of esterification, atom transfer radical polymerization (ATRP), divergent reaction, ring‐opening polymerization (ROP), and coupling reaction on the basis of pentaerythritol. The reaction of pentaerythritol with 2‐bromopropionyl bromide permitted ATRP of styrene (St) to form four‐arm star‐shaped polymer (PSt‐Br)₄. The molecular weights of these polymers could be adjusted by the variation of monomer conversion. Eight‐hydroxyl star‐shaped polymer (PSt‐(OH)₂)₄ was produced by the divergent reaction of (PSt‐Br)₄ with diethanolamine. (PSt‐(OH)₂)₄ was used as the initiator for ROP of ε‐caprolactone (CL) to produce eight‐arm star‐shaped dendrimer‐like copolymer (PSt‐b‐(PCL)₂)₄. The molecular weights of (PSt‐b‐(PCL)₂)₄ increased linearly with the increase of monomer. After the coupling reaction of hydroxyl‐terminated (PSt‐b‐(PCL)₂)₄ with 1‐pyrenebutyric acid, pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer (PSt‐b‐(PCL‐pyrene)₂)₄ was obtained. The eight‐arm star‐shaped dendrimer‐like copolymers presented unique thermal properties and crystalline morphologies, which were different from those of linear poly(ε‐caprolactone) (PCL). Fluorescence analysis indicated that (PSt‐b‐(PCL‐pyrene)₂)₄ presented slightly stronger fluorescence intensity than 1‐pyrenebutyric acid when the pyrene concentration of them was the same. The obtained pyrene‐containing eight‐arm star‐shaped dendrimer‐like copolymer has potential applications in biological fluorescent probe, photodynamic therapy, and optoelectronic devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2788–2798, 2008     

Synthesis of AB3‐type miktoarm star polymers with steroid core via a combination of “Click” chemistry and ring opening polymerization techniques

Well‐defined AB₃‐type miktoarm star‐shaped polymers with cholic acid (CA) core were fabricated with a combination of “click” chemistry and ring opening polymerization (ROP) methods. Firstly, azide end‐functional poly(ethylene glycol) (mPEG), poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(ε‐caprolactone) (PCL) polymers were prepared via controlled polymerization and chemical modification methods. Then, CA moieties containing three OH groups were introduced to these polymers as the end groups via Cu(I)‐catalyzed click reaction between azide end‐functional groups of the polymers ( mPEG‐N₃ , PMMA‐N₃ , PS‐N₃ , and PCL‐N₃ ) and ethynyl‐functional CA under ambient conditions, yielding CA end‐functional polymers ( mPEG‐Cholic , PMMA‐Cholic , PS‐Cholic , and PCL‐Cholic ). Finally, the obtained CA end‐capped polymers were employed as the macroinitiators in the ROP of ε‐caprolactone (ε‐CL) yielding AB₃‐type miktoarm star polymers ( mPEG‐Cholic‐PCL₃ , PMMA‐Cholic‐PCL₃ , and PS‐Cholic‐PCL₃ ) and asymmetric star polymer [ Cholic‐(PCL)₄ ]. The chemical structures of the obtained intermediates and polymers were confirmed via Fourier transform infrared and ¹H nuclear magnetic resonance spectroscopic techniques. Thermal decomposition behaviors and phase transitions were studied in detail using thermogravimetric analysis and differential scanning calorimetry experiments. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3390–3399     

Synthesis,characterization, and micellization of PCL‐g‐PEG copolymers by combination of ROP and “Click” chemistry via “Graft onto” method

Biodegradable and biocompatible PCL‐g‐PEG amphiphilic graft copolymers were prepared by combination of ROP and “click” chemistry via “graft onto” method under mild conditions. First, chloro‐functionalized poly(ε‐caprolactone) (PCL‐Cl) was synthesized by the ring‐opening copolymerization of ε‐caprolactone (CL) and α‐chloro‐ε‐caprolactone (CCL) employing scandium triflate as high‐efficient catalyst with near 100% monomer conversion. Second, the chloro groups of PCL‐Cl were quantitatively converted into azide form by NaN₃. Finally, copper(I)‐catalyzed cycloaddition reaction was carried out between azide‐functionalized PCL (PCL‐N₃) and alkyne‐terminated poly(ethylene glycol) (A‐PEG) to give PCL‐g‐PEG amphiphilic graft copolymers. The composition and the graft architecture of the copolymers were characterized by ¹H NMR, FTIR, and GPC analyses. These amphiphilic graft copolymers could self‐assemble into sphere‐like aggregates in aqueous solution with diverse diameters, which decreased with the increasing of grafting density. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of well‐defined azide‐terminated poly(vinyl alcohol) and their subsequent modification via click chemistry

A new azide‐functionalized xanthate, S‐(4‐azidomethylbenzyl) O‐(2‐methoxyethyl) xanthate, was synthesized and used to mediate the reversible addition fragmentation chain transfer polymerization of vinyl acetate. The polymerization was demonstrated to be controlled, and well‐defined PVAc with α‐azide, ω‐xanthate groups were obtained, the xanthate groups of which were further removed by radical‐induced reduction with lauroyl peroxide in the presence of excess 2‐propanol. Hydrolysis of α‐azide‐terminated PVAc (N₃‐PVAc) led to the formation of the corresponding α‐azide‐terminated PVA (N₃‐PVA). Finally, end‐modification of N₃‐PVA by click chemistry with alkyne‐end‐capped poly(caprolactone) (A‐PCL), alkynyl‐mannose, and alkynyl‐pyrene was carried out to obtain a new block copolymer PCL‐b‐PVA, and two PVA with mannose or pyrene as the end functional groups. The polymers were characterized by gel permeation chromatography, ¹H NMR spectroscopy, and FTIR. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4494–4504, 2009     

Synthesis of ABCD 4‐miktoarm star polymers by combination of RAFT,ROP, and “Click Chemistry”

The ABCD 4‐miktoarm star polymers based on polystyrene (PS), poly(ε‐caprolactone) (PCL), poly(methyl acrylate) (PMA), and poly(ethylene oxide) (PEO) were synthesized and characterized successfully. Using the mechanism transformation strategy, PS with three different functional groups (i.e., hydroxyl, alkyne, and trithiocarbonate), PS‐HEPPA‐SC(S)SC₁₂H₂₅, was synthesized by the reaction of the trithiocarbonate‐terminated PS with 2‐hydroxyethyl‐3‐(4‐(prop‐2‐ynyloxy)phenyl) acrylate (HEPPA) in tetrahydrofuran (THF) solution. Subsequently, the ring‐opening polymerization (ROP) of ε‐caprolactone (CL) was carried out in the presence of stannous(II) 2‐ethylhexanoate and PS‐HEPPA‐SC(S)SC₁₂H₂₅, and then the PS‐HEPPA(PCL)‐SC(S)SC₁₂H₂₅ obtained was used in reversible addition‐fragmentation chain transfer (RAFT) polymerization of methyl acrylate (MA) to produce the ABC 3‐miktoarm star polymer, S(PS)(PCL)(PMA) carrying an alkyne group. The ABCD 4‐miktoarm star polymer, S(PS)(PCL)(PMA)(PEO) was successfully prepared by click reaction of the alkyne group on the HEPPA unit with azide‐terminated PEO (PEO‐N₃). The target polymer and intermediates were characterized by NMR, FTIR, GPC, and DSC. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6641–6653, 2008     

One‐pot preparation of 3‐miktoarm star terpolymers via click [3 + 2] reaction

The preparation of 3‐miktoarm star terpolymers using nitroxide mediated radical polymerization (NMP), ring opening polymerization (ROP), and click reaction [3 + 2] are carried out by applying two types of one‐pot technique. In the first one‐pot technique, NMP of styrene (St), ROP of ε‐caprolactone (ε‐CL), and [3 + 2] click reaction (between azide end‐functionalized poly(ethylene glycol) (PEG‐N₃)/or azide end‐functionalized poly(methyl methacrylate) (PMMA‐N₃) and alkyne) are carried out in the presence of 2‐(hydroxymethyl)‐2‐methyl‐3‐oxo‐3‐(2‐phenyl‐2‐(2,2,6,6‐tetramethylpiperidin‐1‐yloxy)ethoxy) propyl pent‐4‐ynoate, 2 , as an initiator for 48 h at 125 °C (one‐pot/one‐step). As a second technique, NMP of St and ROP of ε‐CL were conducted using 2 as an initiator for 20 h at 125 °C, and subsequently PEG‐N₃ or azide end‐functionalized poly(tert‐butyl acrylate (PtBA‐N₃) was added to the polymerization mixture, followed by a click reaction [3 + 2] for 24 h at room temperature (one‐pot/two‐step). The 3‐miktoarm star terpolymers, PEG‐poly(ε‐caprolactone)(PCL)‐PS, PtBA‐PCL‐PS and PMMA‐PCL‐PS, were recovered by a simple precipitation in methanol without further purification. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3588–3598, 2007     

Synthesis of Novel Core Cross‐Linked Star‐Based Polyrotaxane End‐Capped via “CuAAC” Click Chemistry

The first example of core cross‐linked star (CCS) polyrotaxane was prepared using the poly(ϵ‐caprolactone) (PCL) CCS three‐dimensional (3D) scaffold. The 3D CCS polymer was firstly prepared through the “arm‐first” approach. Then, the “arms” of the resultant PCL CCS polymer were threaded with α‐cyclodextrins (α‐CDs). The threaded α‐CDs were permanently locked by the “click” reaction of terminal alkyne functionalities of the star polymers with the azide‐functionalized end caps to afford the CCS polyrotaxanes. All analytical results confirm the formation of the CCS polyrotaxanes and reveal their characteristics, including fluorescence under UV, a channel‐type crystalline structure, a two‐step thermal decomposition, and a unique core‐shell structure in great contrast to the polymer precursors.     

Micelles possessing mixed cores and thermoresponsive shells fabricated from well‐defined amphiphilic ABC miktoarm star terpolymers

Amphiphilic ABC miktoarm star terpolymers consisting of polystyrene, poly(ε‐caprolactone), and poly(N‐isopropylacrylamide) arms, PS(‐b‐PNIPAM)‐b‐PCL, were synthesized via a combination of atom transfer radical polymerization, ring‐opening polymerization (ROP), and click chemistry. Difunctional PS bearing an alkynyl and a primary hydroxyl moiety at the chain end, PS‐alknyl‐OH, was prepared by reacting azido‐terminated PS with an excess of 3,5‐bis(propargyloxy)benzyl alcohol (BPBA) under click conditions. The subsequent ROP of ε‐caprolactone using PS‐alknyl‐OH macroinitiator afforded PS(‐alkynyl)‐b‐PCL copolymer bearing an alkynyl moiety at the diblock junction point. Target PS(‐b‐PNIPAM)‐b‐PCL amphiphilic ABC miktoarm star terpolymers were then prepared via click reaction between PS(‐alkynyl)‐b‐PCL and an excess of azido‐terminated PNIPAM (PNIPAM‐N₃). The removal of excess PNIPAM‐N₃ was accomplished by “clicking” onto alkynyl‐functionalized Wang resin. All the intermediate and final products were characterized by gel permeation chromatography, ¹H NMR, and FTIR. In aqueous solution, the obtained amphiphilic ABC miktoarm star terpolymer self‐assembles into micelles possessing mixed PS/PCL cores and thermoresponsive shells, which were further characterized by dynamic laser light scattering and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1636–1650, 2009     

Synthesis,self‐assembly and drug‐loading capacity of well‐defined drug‐conjugated amphiphilic A2B2 type miktoarm star copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol)

Well‐defined drug‐conjugated amphiphilic A₂B₂ miktoarm star copolymers [(PCL)₂‐(PEG)₂‐D] were prepared by the combination of controlled ring‐opening polymerization (CROP) and “click” reaction strategy. First, bromide functionalized poly(ε‐caprolactone) (PCL‐Br) with double hydroxyl end groups was synthesized by the CROP of ε‐caprolactone using 2,2‐bis(bromomethyl)propane‐1,3‐diol as a difunctional initiator in the presence of Sn(Oct)₂ at 110 °C. Next, the bromide groups of PCL‐Br were quantitatively converted to azide form by NaN₃ to give PCL‐N₃. Subsequently, the end hydroxyl groups of PCL‐N₃ were capped with ibuprofen as a model drug at room temperature. Finally, copper(I)‐catalyzed cycloaddition reaction between ibuprofen‐conjugated PCL‐N₃ and slightly excess alkyne‐terminated poly(ethylene glycol) (A‐PEG) led to ibuprofen‐conjugated A₂B₂ miktoarm star copolymer [(PCL)₂‐(PEG)₂‐D]. The excess A‐PEG was removed by dialysis. ¹H NMR, FTIR and SEC analyzes confirmed the expected miktoarm star architecture. These amphiphilic miktoarm star copolymers could self‐assemble into multimorphological aggregates in aqueous solution, which were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). In addition, the drug‐loading capacity of these drug‐conjugated miktoarm star copolymers as well as their nondrug‐conjugated analogs were also investigated in detail. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Synthesis and characterization of resorcinarene‐centered amphiphilic A8B4 miktoarm star copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol) by combination of CROP and “click” chemistry

Well‐defined amphiphilic A₈B₄ miktoarm star copolymers with eight poly(ethylene glycol) chains and four poly(ε‐caprolactone) arms (R‐8PEG‐4PCL) were prepared using “click” reaction strategy and controlled ring‐opening polymerization (CROP). First, multi‐functional precursor (R‐8N₃‐4OH) with eight azides and four hydroxyls was synthesized based on the derivatization of resorcinarene. Then eight‐PEG‐arm star polymer (R‐8PEG‐4OH) was prepared through “click” reaction of R‐8N₃‐4OH with pre‐synthesized alkyne‐terminated monomethyl PEG (mPEG‐A) in the presence of CuBr/N,N,N′,N″,N″′‐ pentamethyldiethylenetriamine (PMDETA) in DMF. Finally, R‐8PEG‐4OH was used as tetrafunctional macroinitiator to prepare resorcinarene‐centered A₈B₄ miktoarm star copolymers via CROP of ε‐caprolactone utilizing Sn(Oct)₂ as catalyst at 100 °C. These miktoarm star copolymers could self‐assemble into spherical micelles in aqueous solution with resorcinarene moieties on the hydrophobic/hydrophilic interface, and the particle sizes could be controlled by the ratio of PCL to PEG. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2824–2833.     

Synthesis of well‐defined star‐shaped poly(ε‐caprolactone)/poly(ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry

Well‐defined star‐shaped hydrophobic poly(ε‐caprolactone) (PCL) and hydrophilic poly(ethylene glycol) (PEG) amphiphilic conetworks (APCNs) have been synthesized via the combination of ring opening polymerization (ROP) and click chemistry. Alkyne‐terminated six arm star‐shaped PCL (6‐s‐PCLx‐C?CH) and azido‐terminated PEG (N₃‐PEG‐N₃) are characterized by ¹H NMR and FT‐IR. The swelling degree of the APCNs is determined both in water and organic solvent. This unique property of the conetworks is dependent on the nanophase separation of hydrophilic and hydrophobic phases. The morphology and thermal behaviors of the APCNs are investigated by SEM and DSC respectively. The biocompatibility is determined by water soluble tetrazolium salt reagents (WST‐1) assay, which shows the new polymer networks had good biocompatibility. Through in vitro release of paclitaxel (PTX) and doxorubicin (DOX), the APCNs is confirmed to be promising drug depot materials for sustained hydrophobic and hydrophilic drugs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 407–417     

3‐miktoarm star terpolymers using triple click reactions: Diels–Alder,copper‐catalyzed azide‐alkyne cycloaddition,and nitroxide radical coupling reactions

Well‐defined linear furan‐protected maleimide‐terminated poly(ethylene glycol) (PEG‐MI), tetramethylpiperidine‐1‐oxyl‐terminated poly(ε‐caprolactone) (PCL‐TEMPO), and azide‐terminated polystyrene (PS‐N₃) or ‐poly(N‐butyl oxanorbornene imide) (PONB‐N₃) were ligated to an orthogonally functionalized core ( 1 ) in a two‐step reaction mode through triple click reactions. In a first step, Diels–Alder click reaction of PEG‐MI with 1 was performed in toluene at 110 °C for 24 h to afford α‐alkyne‐α‐bromide‐terminated PEG (PEG‐alkyne/Br). As a second step, this precursor was subsequently ligated with the PCL‐TEMPO and PS‐N₃ or PONB‐N₃ in N,N‐dimethylformamide at room temperature for 12 h catalyzed by Cu(0)/Cu(I) through copper‐catalyzed azide‐alkyne cycloaddition and nitroxide radical coupling click reactions, yield resulting ABC miktoarm star polymers in a one‐pot mode. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of inverse star block copolymer by combination of ATRP,ring opening polymerization,and “click chemistry”

The inverse star block copolymer, (poly(ε‐caprolactone)‐b‐polystyrene)₂‐core‐(poly(ε‐caprolactone)‐b‐polystyrene)₂, [(PCL‐PS)₂‐core‐(PCL‐PS)₂] has been successfully prepared by combination of atom transfer radical polymerization (ATRP), ring opening polymerization (ROP), and “Click Chemistry.” The synthesis includes the following five steps: (1) synthesis of a heterofunctional initiator with two ATRP initiating groups and two hydroxyl groups; (2) formation of (Br‐PS)₂‐core‐(OH)₂ via ATRP of styrene; (3) preparation of the (PCL‐PS)₂‐core‐(OH)₂ through “click” reaction of the α‐propargyl, ω‐acetyl terminated PCL with (N₃‐PS)₂‐core‐(OH)₂ which was prepared by transformation of the terminal bromine groups in (Br‐PS)₂‐core‐(OH)₂ into azide groups; (4) the ROP of CL using (PCL‐PS)₂‐core‐(OH)₂ as macroinitiator to form (PCL‐PS)₂‐core‐(PCL‐OH)₂; and (5) preparation of the (PCL‐PS)₂‐core‐(PCL‐PS)₂ through the ATRP of styrene using (PCL‐PS)₂‐core‐(PCL‐Br)₂ as macroinitiator which was prepared by reaction of the terminal hydroxyl groups at the end of the PCL chains with 2‐bromoisobutyryl bromide. The characterization data support structures of the inverse star block copolymer and the intermediates. The differential scanning calorimeter results and polarized optical microscope observation showed that the intricate structure of the inverse star block copolymer greatly restricted the movement of the PS segments and PCL segments, resulted in the increase of the glass transition temperature of PS segments and the decrease of crystallization ability of PCL segments. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7757–7772, 2008     

Dendrimer‐like miktoarm star terpolymers: A3‐(B‐C)3 via click reaction strategy

Two samples of dendrimer‐like miktoarm star terpolymers: (poly(tert‐butyl acrylate))₃‐(polystyrene‐poly(ε‐caprolactone))₃ (PtBA)₃‐(PS‐PCL)₃, and (PS)₃‐(PtBA‐poly(ethylene glycol)₃ were prepared using efficient Cu catalyzed Huisgen cycloaddition (click reaction). As a first step, azido‐terminated 3‐arm star polymers PtBA and PS as core (A) were synthesized by atom transfer radical polymerization (ATRP) of tBA and St, respectively, followed by the conversion of bromide end group to azide. Secondly, PS‐PCL and PtBA‐PEG block copolymers with alkyne group at the junction as peripheral arms (B‐C) were obtained via multiple living polymerization mechanisms such as nitroxide mediated radical polymerization (NMP) of St, ring opening polymerization (ROP) of ε‐CL, ATRP of tBA. Thus obtained core and peripheral arms were linked via click reaction to give target (A)₃‐(B‐C)₃ dendrimer‐like miktoarm star terpolymers. (PtBA)₃‐(PS‐PCL)₃ and (PS)₃‐(PEG‐PtBA)₃ have been characterized by GPC, DSC, AFM, and SAXS measurements. (PtBA)₃‐(PS‐PCL)₃ did not show any self‐organization with annealing due to the miscibility of the peripheral arm segments. In contrast, the micro‐phase separation of the peripheral arm segments in (PS)₃‐(PtBA‐PEG)₃ resulted in self‐organized phase‐separated morphology with a long period of ～ 13 nm. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5916–5928, 2008     

H‐shaped (ABCDE type) quintopolymer via click reaction [3 + 2] strategy

H‐shaped quintopolymer containing different five blocks: poly(ε‐caprolactone) (PCL), polystyrene (PS), poly(ethylene glycol) (PEG), and poly(methyl methacrylate) (PMMA) as side chains and poly(tert‐butyl acrylate) (PtBA) as a main chain was simply prepared from a click reaction between azide end‐functionalized PCL‐PS‐PtBA 3‐miktoarm star terpolymer and PEG–PMMA‐block copolymer with alkyne at the junction point, using Cu(I)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as a catalyst in DMF at room temperature for 20 h. The H‐shaped quintopolymer was obtained with a number–average molecular weight (M_n) around 32,000 and low polydispersity index (M_w/M_n) 1.20 as determined by GPC analysis in THF using PS standards. The click reaction efficiency was calculated to have 60% from ¹H NMR spectroscopy. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4459–4468, 2008     

Synthesis and characterization of novel resorcinarene‐centered amphiphilic star‐block copolymers consisting of eight ABA triblock arms by combination of ROP,ATRP, and click chemistry

Novel amphiphilic eight‐arm star triblock copolymers, star poly(ε‐caprolactone)‐block‐poly(acrylic acid)‐block‐poly(ε‐caprolactone)s (SPCL‐PAA‐PCL) with resorcinarene as core moiety were prepared by combination of ROP, ATRP, and “click” reaction strategy. First, the hydroxyl end groups of the predefined eight‐arm SPCLs synthesized by ROP were converted to 2‐bromoesters which permitted ATRP of tert‐butyl acrylate (tBA) to form star diblock copolymers: SPCL‐PtBA. Next, the bromide end groups of SPCL‐PtBA were quantitatively converted to terminal azides by NaN₃, which were combined with presynthesized alkyne‐terminated poly(ε‐caprolactone) (A‐PCL) in the presence of Cu(I)/N,N,N′,N″,N″‐pentamethyldiethylenetriamine in DMF to give the star triblock copolymers: SPCL‐PtBA‐PCL. ¹H NMR, FTIR, and SEC analyses confirmed the expected star triblock architecture. The hydrolysis of tert‐butyl ester groups of the poly(tert‐butyl acrylate) blocks gave the amphiphilic star triblock copolymers: SPCL‐PAA‐PCL. These amphiphilic star triblock copolymers could self‐assemble into spherical micelles in aqueous solution with the particle size ranging from 20 to 60 nm. Their micellization behaviors were characterized by dynamic light scattering and transmission electron microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2905–2916, 2009     

One‐pot synthesis of ABC miktoarm star terpolymers by coupling ATRP,ROP, and click chemistry techniques

We report on the one‐pot synthesis of well‐defined ABC miktoarm star terpolymers consisting of poly(2‐(dimethylamino)ethyl methacrylate), poly(ε‐caprolactone), and polystyrene or poly(ethylene oxide) arms, PS(‐b‐PCL)‐b‐PDMA and PEO (‐b‐PCL)‐b‐PDMA, taking advantage of the compatibility and mutual tolerability of reaction conditions (catalysts and monomers) employed for atom transfer radical polymerization (ATRP), ring‐opening polymerization (ROP), and click reactions. At first, a novel trifunctional core molecule bearing alkynyl, hydroxyl group, and bromine moieties, alkynyl(? OH)? Br, was synthesized via the esterification reaction of 5‐ethyl‐5‐hydroxymethyl‐2,2‐dimethyl‐1,3‐dioxane with 4‐oxo‐4‐(prop‐2‐ynyloxy)butanoic acid, followed by deprotection and monoesterification of alkynyl(? OH)₂ with 2‐bromoisobutyryl bromide. In the presence of trifunctional core molecule, alkynyl(? OH)? Br, and CuBr/PMDETA/Sn(Oct)₂ catalytic mixtures, target ABC miktoarm star terpolymers, PS(‐b‐PCL)‐b‐PDMA and PEO(‐b‐PCL)‐b‐PDMA, were successfully synthesized in a one‐pot manner by simultaneously conducting the ATRP of 2‐(dimethylamino)ethyl methacrylate (DMA), ROP of ε‐caprolactone (ε‐CL), and the click reaction with azido‐terminated PS (PS‐N₃) or azido‐terminated PEO (PEO‐N₃). Considering the excellent tolerability of ATRP to a variety of monomers and the fast expansion of click chemistry in the design and synthesis of polymeric and biorelated materials, it is quite anticipated that the one‐pot concept can be applied to the preparation of well‐defined polymeric materials with more complex chain architectures. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3066–3077, 2009     

Multiarm star block and multiarm star mixed‐block copolymers via azide‐alkyne click reaction

The synthesis of multiarm star block (and mixed‐block) copolymers are efficiently prepared by using Cu(I) catalyzed azide‐alkyne click reaction and the arm‐first approach. α‐Silyl protected alkyne polystyrene (α‐silyl‐alkyne‐PS) was prepared by ATRP of styrene (St) and used as macroinitiator in a crosslinking reaction with divinyl benzene to successfully give multiarm star homopolymer with alkyne periphery. Linear azide end‐functionalized poly(ethylene glycol) (PEG‐N₃) and poly (tert‐butyl acrylate) (PtBA‐N₃) were simply clicked with the multiarm star polymer described earlier to form star block or mixed‐block copolymers in N,N‐dimethyl formamide at room temperature for 24 h. Obtained multiarm star block and mixed‐block copolymers were identified by using ¹H NMR, GPC, triple detection‐GPC, atomic force microscopy, and dynamic light scattering measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 99–108, 2010