Construction of PIB‐b‐PDEAEMA well‐defined amphiphilic diblock copolymers via sequential living carbocationic and RAFT polymerization

A series of well‐defined amphiphilic diblock copolymers consisting of hydrophobic polyisobutylene (PIB) and hydrophilic poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) segments was synthesized via the combination of living carbocationic polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization. Living carbocationic polymerization of isobutylene followed by end‐capping with 1,3‐butadiene was first performed at ?70 °C to give a well‐defined allyl‐Cl‐terminated PIB with a low polydispersity (M_w/M_n =1.29). This end‐functionalized PIB was further converted to a macromolecular chain transfer agent for mediating RAFT block copolymerization of 2‐(diethylamino)ethyl methacrylate at 60 °C in tetrahydrofuran to afford the target well‐defined PIB‐b‐PDEAEMA diblock copolymers with narrow molecular weight distributions (M_w/M_n ≤1.22). The self‐assembly behavior of these amphiphilic diblock copolymers in aqueous media was investigated by fluorescence spectroscopy and transmission electron microscope, and furthermore, their pH‐responsive behavior was studied by UV‐vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1478–1486     

Polymethylene‐b‐polystyrene diblock copolymer: Synthesis,property, and application

The design and synthesis of well‐defined polymethylene‐b‐polystyrene (PM‐b‐PS, M_n = 1.3 × 10⁴–3.0 × 10⁴ g/mol; M_w/M_n (GPC) = 1.08–1.18) diblock copolymers by the combination of living polymerization of ylides and atom transfer radical polymerization (ATRP) was successfully achieved. The ¹H NMR spectrum and GPC traces of PM‐b‐PS indicated the successful extension of PS segment on the PM macroinitiator. The micellization behavior of such diblock copolymers in tetrahydrofuran were characterized by dynamic light scattering (DLS) and atomic force microscopy (AFM) techniques. The average aggregate sizes of PM‐b‐PS diblock copolymers with the same length of PM segment in tetrahydrofuran solution (1.0 mg mL^?1) increases from 104.2 nm to 167.7 nm when the molecular weight of PS segment increases. The spherical precipitated aggregates of PM‐b‐PS diblock copolymers with an average diameter of 600 nm were observed by AFM. Honeycomb porous films with the average diameter of 3.0 μm and 6.0 μm, respectively, were successfully fabricated using the solution of PM‐b‐PS diblock copolymers in carbon disulfide via the breath‐figure (BF) method under a static humid condition. The cross‐sections of low density polyethylene (LDPE)/polystyrene (PS)/PM‐b‐PS and LDPE/polycarbonate (PC)/PM‐b‐PS blends were observed by scanning electron microscope and reveal that the PM‐b‐PS diblock copolymers are effective compatilizers for LDPE/PS and LDPE/PC blends. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1894–1900, 2010     

Photo‐ and pH‐Responsive Polycarbonate Block Copolymer Prodrug Nanomicelles for Controlled Release of Doxorubicin

Photo/pH dual‐responsive amphiphilic diblock copolymers with alkyne functionalized pendant o‐nitrobenzyl ester group are synthesized using poly(ethylene glycol) as a macroinitiator. The pendant alkynes are functionalized as aldehyde groups by the azide‐alkyne Huisgen cycloaddition. The anticancer drug doxorubicin (DOX) molecules are then covalently conjugated through acid‐sensitive Schiff‐base linkage. The resultant prodrug copolymers self‐assemble into nanomicelles in aqueous solution. The prodrug nanomicelles have a well‐defined morphology with an average size of 20–40 nm. The dual‐stimuli are applied individually or simultaneously to study the release behavior of DOX. Under UV light irradiation, nanomicelles are disassembled due to the ONB ester photocleavage. The light‐controlled DOX release behavior is demonstrated using fluorescence spectroscopy. Due to the pH‐sensitive imine linkage the DOX molecules are released rapidly from the nanomicelles at the acidic pH of 5.0, whereas only minimal amount of DOX molecules is released at the pH of 7.4. The DOX release rate is tunable by applying the dual‐stimuli simultaneously. In vitro studies against colon cancer cells demonstrate that the nanomicelles show the efficient cellular uptake and the intracellular DOX release, indicating that the newly designed copolymers with dual‐stimuli‐response have significant potential applications as a smart nanomedicine against cancer.     

Polyisobutylene‐b‐Poly(N,N‐diethylacrylamide) well‐defined amphiphilic diblock copolymer: Synthesis and thermo‐responsive phase behavior

Polyisobutylene‐b‐poly(N,N‐diethylacrylamide) (PIB‐b‐PDEAAm) well‐defined amphiphilic diblock copolymers were synthesized by sequential living carbocationic polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization. The hydrophobic polyisobutylene segment was first built by living carbocationic polymerization of isobutylene at ?70 ° C followed by multistep transformations to give a well‐defined (M_w/M_n = 1.22) macromolecular chain transfer agent, PIB‐CTA. The hydrophilic poly(N,N‐diethylacrylamide) block was constructed by PIB‐CTA mediated RAFT polymerization of N,N‐diethylacrylamide at 60 ° C to afford the desired well‐defined PIB‐b‐PDEAAm diblock copolymers with narrow molecular weight distributions (M_w/M_n ≤1.26). Fluorescence spectroscopy, transmission electron microscope, and dynamic light scattering (DLS) were employed to investigate the self‐assembly behavior of PIB‐b‐PDEAAm amphiphilic diblock copolymers in aqueous media. These diblock copolymers also exhibited thermo‐responsive phase behavior, which was confirmed by UV‐Vis and DLS measurements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1143–1150     

Macrophase‐separation in binary blends of symmetric polystyrene‐polybutadiene diblock copolymers

Binary blends of compositionally symmetric polystyrene‐polybutadiene diblock copolymers are investigated as a function of chain length ratio and blend composition using small‐angle neutron scattering. Three different low molar mass copolymers were blended with a high molar mass copolymer. The results are related to the theoretical phase diagram put forward by M. W. Matsen (J. Chem. Phys. 103 , 3268 (1995)). The conditions for macrophase‐separation are established, an observed asymmetry of the lamellae rich in long copolymers is discussed and the variation of the lamellar thickness with the volume fraction of short chains in the one‐phase state is compared with theoretical predictions.     

Self‐Assembly in Water of Poly(acrylic acid)‐Based Diblock Copolymers Synthesized by Nitroxide‐Mediated Polymerization

Summary: Amphiphilic diblock copolymers consisting of a hydrophilic block, poly(acrylic acid), and a hydrophobic block, polystyrene, were synthesized by direct nitroxide‐mediated polymerization using the PS block as a macro‐initiator for the first time. Several techniques were used to characterize the amphiphilic block copolymers (size exclusion chromatography, NMR spectroscopy). The proposed method can lead to samples with a broad range of composition and molar mass. Preliminary studies of their self‐assembly in aqueous medium using fluorescence spectroscopy and small‐angle neutron scattering are presented.

Schematic of the formation of the PS‐b‐PAA block copolymers and their micellization in aqueous media.     

Novel perfluorocyclobutyl aryl ether‐based well‐defined amphiphilic block copolymer

A series of fluorine‐containing amphiphilic diblock copolymers comprising hydrophobic poly(p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) (PTPFCBPMA) and hydrophilic poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) segments were synthesized via successive reversible addition fragmentation chain transfer (RAFT) polymerizations. RAFT homopolymerization of p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate was first initiated by 2,2′‐azobisisobutyronitrile using cumyl dithiobenzoate as chain transfer agent, and the results show that the procedure was conducted in a controlled way as confirmed by the fact that the number‐average molecular weights increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.30. Dithiobenzoate‐capped PTPFCHPMA homopolymer was then used as macro‐RAFT agent to mediate RAFT polymerization of 2‐(diethylamino)ethyl methacrylate, which afforded PTPFCBPMA‐b‐PDEAEMA amphiphilic diblock copolymers with different block lengths and narrow molecular weight distributions (M_w/M_n ≤ 1.28). The critical micelle concentrations of the obtained amphiphilic diblock copolymers were determined by fluorescence spectroscopy technique using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of the formed micelles were investigated by transmission electron microscopy and dynamic light scattering, respectively. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Thermosensitive diblock copolymers with designed molecular weight distribution: Synthesis by continuous living cationic polymerization and micellization behavior

The synthesis of diblock copolymers with designed molecular weight distributions (MWDs) was successfully demonstrated in a continuous living cationic polymerization system using simple equipment. The control of MWDs was achieved by gradually feeding a polymerization reaction mixture into a terminating agent. As thermosensitive diblock copolymers, poly(vinyl ethers) containing a thermosensitive segment with oxyethylene side chains and a hydrophilic segment were prepared. The polymerization was carried out in a gas‐tight microsyringe, and the polymerization mixture was added continuously into methanol during the second‐stage polymerization. The self‐association behavior of the resulting diblock copolymers was evaluated by dynamic light scattering in water. MWD‐designed polymers with thermosensitive segments that varied continuously in length and hydrophilic segments of nearly uniform lengths formed micelles with a broad size distribution. Conversely, polymers with nearly uniform thermosensitive segments and hydrophilic segments of different lengths formed micelles with a narrow size distribution, as observed with conventional narrow MWD diblock copolymers. Thus, the MWD of the thermosensitive segment proved a decisive factor in achieving fine control of self‐association. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2212–2221, 2008     

Syntheses of polyolefin‐based stereoregular diblock copolymers for self‐assembled nanostructures

The preparation of polyolefin‐based stereoregular diblock copolymers by postpolymerization of ethenyl‐capped syndiotactic polypropylene‐based propylene/norbornene copolymer (sPP‐based P‐N copolymer) led to the successful generation of a structurally uniform stereoregular diblock copolymer for self‐assembly studies. The ethenyl‐capped prepolymer was prepared by conducting propylene/norbornene copolymerization in the presence of Me₂C(Cp)(Flu)ZrCl₂/MAO. Ozonolysis of ethenyl‐capped sPP‐based P‐N copolymer provided the formyl group end‐capped, end‐functionalized prepolymer with a quantitative functional group conversion ratio. Subsequently, connecting the formyl end‐group of the stereoregular prepolymer by coupling with living anionic polystyrene resulted in the high yield production of stereoregular diblock copolymer (sPP‐based P‐N‐block‐polystyrene), which is difficult to prepare by other methods. The resulting stereoregular diblock copolymer possesses precise chemical architecture to self‐organize into consistent nanostructures as evidenced by transmission electron microscopy and small angle X‐ray scattering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4843–4856, 2008     

Synthesis of hybrid dendritic‐linear block copolymers with dendritic initiators prepared by convergent living anionic polymerization

Hybrid dendritic‐linear block copolymers were made in one‐pot by convergent living anionic polymerization. Dendritic polystyrene macroinitiators were synthesized by slowly adding a mixture of either vinylbenzyl chloride (VBC) or 4‐(chlorodimethylsilyl)styrene (CDMSS) and styrene (1 : 10 molar ratio of coupling agent to styrene) to a solution of living polystyryllithium. The addition was ceased prior to the addition of a stoichiometric amount of coupling agent to retain a living chain end. To the living dendritically branched polystyrene was then added either styrene or isoprene to polymerize a linear block from the dendritic polystyrene. The resulting copolymers were characterized by gel permeation chromatography coupled with multiangle laser light scattering (GPC‐MALLS), which clearly demonstrated the formation of diblock copolymers. The diblock copolymers were further characterized by ¹H NMR, which showed the presence of the two blocks in the case of dendritic polystyrene‐block‐linear polyisoprene. The measurement of intrinsic viscosity showed that the dilute solution properties of the block copolymers are greatly influenced by the dendritic portion. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 152–161, 2001     

Effect of polystyrene‐b‐poly(ethylene oxide) on self‐assembly of polystyrene‐b‐poly(N‐isopropylacrylamide) in aqueous solution

Mixed micelles of polystyrene‐b‐poly(N‐isopropylacrylamide) (PS‐b‐PNIPAM) and two polystyrene‐b‐poly(ethylene oxide) diblock copolymers (PS‐b‐PEO) with different chain lengths of polystyrene in aqueous solution were prepared by adding the tetrahydrofuran solutions dropwise into an excess of water. The formation and stabilization of the resultant mixed micelles were characterized by using a combination of static and dynamic light scattering. Increasing the initial concentration of PS‐b‐PEO in THF led to a decrease in the size and the weight average molar mass (〈M_w〉) of the mixed micelles when the initial concentration of PS‐b‐ PNIPAM was kept as 1 × 10^?3 g/mL. The PS‐b‐PEO with shorter PS block has a more pronounced effect on the change of the size and 〈M_w〉 than that with longer PS block. The number of PS‐b‐PNIPAM in each mixed micelle decreased with the addition of PS‐b‐PEO. The average hydrodynamic radius 〈R_h〉 and average radius of gyration 〈R_g〉 of pure PS‐b‐PNIPAM and mixed micelles gradually decreased with the increase in the temperature. Both the pure micelles and mixed micelles were stable in the temperature range of 18 °C–39 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1168–1174, 2010     

Synthesis,characterization, and properties of tunable thermosensitive amphiphilic dendrimer‐star copolymers with Y‐shaped arms

Novel and well‐defined amphiphilic dendrimer‐star copolymer poly(ε‐caprolactone)‐block‐(poly(2‐(2‐methoxyethoxy)ethylmethacrylate‐co‐oligo(ethylene glycol) methacrylate))₂ with Y‐shaped arms were synthesized by the combination of ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The investigation of thermal properties and the analysis of crystalline morphology indicate that the high‐branched structure of dendrimer‐star copolymers with Y‐shaped arms and the presence of amorphous P(MEO₂MA‐co‐OEGMA) segments together led to the complete destruction of crystallinity of the PCL segments in the dendrimer‐star copolymer. In addition, the hydrophilicity–hydrophobicity transition of the dendrimer‐star copolymer film can be achieved by altering the external temperatures. The amphiphilic copolymers can self‐assemble into spherical nanomicelles in water. Because the lower critical solution temperature of the copolymers can be adjusted by varying the ratio of MEO₂MA and OEGMA, the tunable thermosensitive properties can be observed by transmittance, dynamic laser light scattering, and transmission electron microscopy (TEM). The release rate of model drug chlorambucil from the micelles can be effectively controlled by changing the external temperatures, which indicates that these unique high‐branched amphiphilic copolymers have the potential applications in biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and self‐assembly of thermosensitive double‐hydrophilic poly(N‐vinylcaprolactam)‐b‐poly(N‐vinyl‐2‐pyrrolidone) diblock copolymers

We report on novel diblock copolymers of poly(N‐vinylcaprolactam) (PVCL) and poly(N‐vinyl‐2‐pyrrolidone) (PVPON) (PVCL‐b‐PVPON) with well‐defined block lengths synthesized by the MADIX/reversible addition‐fragmentation chain transfer (RAFT) process. We show that the lower critical solution temperatures (LCST) of the block copolymers are controllable over the length of PVCL and PVPON segments. All of the diblock copolymers dissolve molecularly in aqueous solutions when the temperature is below the LCST and form spherical micellar or vesicular morphologies when temperature is raised above the LCST. The size of the self‐assembled structures is controlled by the molar ratio of PVCL and PVPON segments. The synthesized homopolymers and diblock copolymers are demonstrated to be nontoxic at 0.1–1 mg mL^?1 concentrations when incubated with HeLa and HEK293 cancer cells for various incubation times and have potential as nanovehicles for drug delivery. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2725–2737     

Environmentally responsive micelles from polystyrene–poly[bis(potassium carboxylatophenoxy)phosphazene] block copolymers

Amphiphilic diblock copolymers that contained hydrophilic poly[bis(potassium carboxylatophenoxy)phosphazene] segments and hydrophobic polystyrene sections were synthesized via the controlled cationic polymerization of Cl₃P?NSiMe₃ with a polystyrenyl–phosphoranimine as a macromolecular terminator. These block copolymers self‐associated in aqueous media to form micellar structures which were investigated by fluorescence spectroscopy, dynamic light scattering, and transmission electron microscopy. The size and shape of the micelles were not affected by the introduction of different monovalent cations (Li⁺, K⁺, Na⁺, and Cs⁺) into the stable micellar solutions. However, exposure to divalent cations induced intermicellar crosslinking through carboxylate groups, which caused precipitation of the ionically crosslinked aggregates from solution. This micelle‐coupling behavior was reversible: the subsequent addition of monovalent cations caused the redispersion of the polystyrene‐block‐poly[bis(potassium carboxylatophenoxy)phosphazene] (PS–KPCPP) block copolymers into a stable micellar solution. Aqueous micellar solutions of PS–KPCPP copolymers also showed pH‐dependent behavior. These attributes make PS–KPCPP block copolymers suitable for studies of guest retention and release in response to ion charge and pH. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2912–2920, 2005     

Diblock copolymers of polystyrene‐b‐poly(1,3‐cyclohexadiene) exhibiting unique three‐phase microdomain morphologies

The synthesis and molecular characterization of a series of conformationally asymmetric polystyrene‐block‐poly(1,3‐cyclohexadiene) (PS‐b‐PCHD) diblock copolymers (PCHD: ～90% 1,4 and ～10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ ?_PS ≤ 0.91) was studied by transmission electron microscopy and small‐angle X‐ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD‐1,4)–shell(PCHD‐1,2) cylinders in PS matrix and three‐phase (PS, PCHD‐1,4, PCHD‐1,2) four‐layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strong dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS‐b‐PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1564–1572     

Synthesis and characterization of fluorine‐containing PAA‐b‐PTPFCBPMA amphiphilic block copolymer

A series of perfluorocyclobutyl (PFCB) aryl ether‐based amphiphilic diblock copolymers containing hydrophilic poly(acrylic acid) (PAA) and fluorophilic poly(p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) segments were synthesized via successive atom transfer radical polymerization (ATRP). 2‐MBP‐initiated and CuBr/N,N,N′,N′,N″‐pentamethyldiethylenetriamine‐catalyzed ATRP homopolymerization of the PFCB‐containing methacrylate monomer, p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate, can be performed in a controlled mode as confirmed by the fact that the number‐average molecular weights (M_n) increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.38. The block copolymers with narrow molecular weight distributions (M_w/M_n ≤ 1.36) were synthesized by ATRP using Br‐end‐functionalized poly(tert‐butyl acrylate) (PtBA) as macroinitiator followed by the acidolysis of hydrophobic PtBA block into hydrophilic PAA segment. The critical micelle concentrations of the amphiphilic diblock copolymers in different surroundings were determined by fluorescence spectroscopy using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of the micelles were investigated by transmission electron microscopy and dynamic laser light scattering, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Improving mechanical properties and chemical resistance of ink‐jet printer color filter by using diblock polymeric dispersants

The diblock copolymers of polystyrene and poly(tert‐butyl acrylate) (PSt‐b‐PtBA) with various molecular weights and hydrophobic/hydrophilic (styrene/acrylic acid) chain length were prepared by atom transfer radical polymerization (ATRP). Selective hydrolysis of the diblock copolymers (PSt‐b‐PtBA) resulted in amphiphilic block copolymers of polystyrene and poly(acrylic acid) (PSt‐b‐PAA). The amphiphilic block copolymers of PSt‐b‐PAA with average molecular weight (M_n) <7500 were proved to be critical in dispersing the pigments of UV curable ink‐jet inks for manufacturing the color filter. Incorporating DB2 diblock copolymer dispersants with styrene/acrylic acid ratio at 1.5 allowed more UV curable compositions in the red and blue inks without deteriorating pigment dispersing stability and jetting properties of the ink‐jet inks. The ink drops can be precisely ejected into the tiny color area. Better properties of the cured red stripe such as nanoindentation hardness and chemical resistance were found. The competing absorption of UV light by the blue pigment hindered the through cure of monomers near the interface between glass substrate and the blue stripe. This leads to lower hardness and poor chemical resistance of the UV cured blue stripe. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3337–3353, 2005     

Light‐driven and aggregation‐induced emission from side‐chain azoindazole polymers

The well‐defined azoindazole‐containing homopolymer, poly(6‐{6‐[(4‐dimethylamino) phenylazo]‐indazole}‐hexyl methacrylate) (PDHMA), and amphiphilic diblock copolymer, poly({6‐[6‐(4‐dimethylamino)phenylazo]‐indazole}‐hexyl methacrylate)‐b‐poly(2‐(dimethylamino)ethylmethacrylate) (PDHMA_m‐b‐PDMAEMA_n), were successfully prepared via reversible addition‐fragmentation chain transfer polymerization technique. The homopolymer and amphiphilic diblock copolymer in CH₂Cl₂ exhibited intense fluorescence emission accompanied by trans–cis photoisomerization of azoindazole group under UV irradiation. The experiment results indicated that the intense fluorescence emission may be attributed to an inhibition of photoinduced electron transfer of the cis form of azoindazole. On the other hand, the intense fluorescence emission of amphiphilic diblock copolymers in water‐tetrahydrofuran mixture was observed, which increased with the volume ratio of water in the mixed solvent. The self‐aggregation behaviors of three amphiphilic diblock copolymers were examined by transmission electron microscopy, laser light scattering, and UV–vis spectra. The restriction of intramolecular rotation of the azoindazole groups in aggregates was considered as the main cause of aggregation‐induced fluorescence emission. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Amphiphilic diblock copolymers bearing pendant aromatic acetal groups: Synthesis and tunable pH‐triggered assembly/disassembly transition behavior

A novel aromatic acetal‐based acid‐labile monomer 2‐phenyl‐5‐ethyl‐5‐acryloxymethyl‐1,3‐dioxacyclohexane (HEDPA) was synthesized and polymerized by reversible addition fragmentation chain transfer (RAFT) polymerization using alkynyl functional chain transfer agent (CTA‐Alk). Afterward, a series of amphiphilic diblock copolymers composed of fixed hydrophobic poly(2‐phenyl‐5‐ethyl‐5‐acryloxymethyl‐1,3‐dioxacyclohexane) (PDAEP) segments and various lengths of hydrophilic mPEG segments were prepared through click reaction between alkynyl‐terminated PDAEP and azido‐terminated mPEG. The self‐assembly behaviors of the diblock copolymers were investigated by dynamic light scattering (DLS), transmission electron microscopy (TEM), fluorescence spectroscopy, and ¹H NMR. These results indicated that the diblock copolymers could self‐assemble into nano‐sized micelles with PDAEP cores and PEG coronas in aqueous solution. DLS, fluorescence spectroscopy and UV–vis spectroscopy were used to monitor the pH‐triggered assembly/disassembly transition of the micelles. These results showed that the assembly/disassembly transition behaviors of the diblock copolymers micelles can be adjusted by changing the lengths of the mPEG segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1537–1547     

Synthesis and characterization of well‐defined [polystyrene‐b‐poly(2‐vinylpyridine)]n star‐block copolymers with poly(2‐vinylpyridine) corona blocks

This article describes the synthesis and characterization of [polystyrene‐b‐poly(2‐vinylpyridine)]_n star‐block copolymers with the poly(2‐vinylpyridine) blocks at the periphery. A two‐step living anionic polymerization method was used. Firstly, oligo(styryl)lithium grafted poly(divinylbenzene) cores were used as multifunctional initiators to initiate living anionic polymerization of styrene in benzene at room temperature. Secondly, vinylpyridine was polymerized at the periphery of these living (polystyrene)_n stars in tetrahydrofuran at ?78 °C. The resulting copolymers were characterized using size exclusion chromatography, multiangle laser light scattering, ¹H NMR, elemental analysis, and intrinsic viscosity measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3949–3955, 2007