Controlled radical polymerization of p-(iodomethyl)styrene—a route to branched and star-like structures

p-(Iodomethyl)styrene was polymerized under the action of a radical initiator (AIBN). The polymerization proceeds with degenerative chain transfer and leads to well defined branched polymers with functional primary and secondary iodomethyl groups as revealed by NMR studies. The obtained polymer can be further used as macroinitiator for radical polymerization of styrene. This polymerization proceeds in controlled way to polystyrene star polymers with reactive groups at the end of their arms. The characterization of branched and star structures was performed by NMR and GPC with absolute molar mass detection (MALLS).     

Strain-promoted azide-alkyne cycloaddition “click” as a conjugation tool for building topological polymers

Strain-promoted azide-alkyne cycloaddition “click” reaction (SPAAC) was successfully used as a tool in synthesis of star polymers by grafting onto approach. The application of SPAAC method in star polymer synthesis was investigated for coupling reaction of the dibenzocyclooctyne (DIBO) end group of polystyrene (PS) and poly(ethylene glycol) (PEG) with coupling agents bearing 2, 3, or 4 azido groups. Firstly, well-defined linear DIBO-terminated PS was obtained by atom transfer radical polymerization (ATRP) of styrene using a DIBO containing ATRP initiator and linear DIBO-terminated PEG was obtained by terminal functionalization of PEG monomethyl ether (PEG-OH). Then a series of star PS and PEG bearing two, three and four arms were prepared respectively by subjecting SPAAC coupling reaction between the linear polymer-DIBO and the azido tethered core molecules at 30 °C without catalyst. The obtained star PS showed a well-defined structure after fractional precipitation to remove slightly excess linear polymers, and all the star polymers were characterized via Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance spectroscopy (¹H NMR), size exclusion chromatography (SEC) and matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS).     

Synthesis,characterization and surface properties of star‐shaped polymeric surfactants with polyhedral oligomeric silsesquioxane core

Star‐shaped amphiphilic polymeric surfactants comprising a hydrophobic polyhedral oligomeric silsesquioxane (POSS) core and hydrophilic poly(ethylene glycol) (PEG) arms with various chain lengths are successfully synthesized using copper(I)‐catalysed azide–alkyne cycloaddition (CuAAC) click reaction. Their chemical structures and molecular characteristics are clearly confirmed using Fourier transform infrared and ¹H NMR spectroscopies and gel permeation chromatography, and no homopolymer is found after CuAAC click reaction. Aqueous solutions of these star‐shaped polymers have been investigated using atomic force and transmission electron microscopies and dynamic light scattering studies and it is found that they can self‐assemble into micelles. The sizes of the micelles can be adjusted by the length of the PEG arms, where longer chains not only lead to increased micelle sizes, but also reduce the contact angle values. Moreover, the melting points and root mean square roughness of the obtained star‐shaped polymers are slightly increased on increasing the chain length of the PEG arms. © 2017 Society of Chemical Industry     

Environmentally responsive amphiphilic cationic block copolymers synthesized by 2,2,6,6‐Tetramethylpiperidinyloxy mediated living free‐radical polymerization

Polychloromethylstyrene (PCMS)‐block‐polystyrene (PS) copolymers were prepared by controlled free‐radical polymerization in the presence of 2,2,6,6‐tetramethylpiperidinooxy and 2,2′‐azobisisobutyronitrile (AIBN) initiator. The PCMS‐b‐PS copolymers had narrow molecular weight distributions, and the block lengths were controlled by the reaction time and the molar ratios of chloromethylstyrene/AIBN and styrene/PCMS macroinitiator. The block copolymers were further quaternized with triethylamine. The amphiphilic cationic block copolymers formed colloidal particles; the effects of the pH value, salt concentration, and solvent polarity on the particle size were investigated with a dynamic light scattering analyzer. The average colloid size increased with increasing pH value and salt concentration. This implied that the colloid formed a protonated hydrophilic shell and hydrophobic styrene core in water. Furthermore, with the addition of tetrahydrofuran to the aqueous solution, the styrene segments in the core could be inverted to the outside of the colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Core-shell polyacrylate and polystyrene-block-polyacrylate stars

The polymerization of p-(iodomethyl)styrene (PIMS) yields well-defined branched polymers with reactive iodomethyl groups. The branched poly[p-(iodomethyl)styrene] was used as the transfer agent in the iodine mediated radical polymerization of vinyl monomers. The polymerization proceeds in a controlled way and yields polystyrene and poly(t-butyl acrylate) star polymers with reactive groups at the end of their arms. Polymers so obtained were also used to prepare stars with block copolymer arms: polystyrene-block-poly(t-butyl acrylate). The characterization of star structures was performed by NMR and gel permeation chromatography with absolute molar mass detection (MALLS). Preliminary characterization of the thermal properties of these novel materials is reported.     

Chemozymatic synthesis and characterization of H-shaped triblock copolymer

The synthesis of well-defined H-shaped block copolymer based on the enzymatic ring-opening polymerization (eROP) and atom transfer radical polymerization (ATRP) is described. The dihydroxyl polycaprolactone (PCL) was synthesized by the eROP of ε-caprolactone (ε-CL) in the presence biocatalyst Novozyme 435 and initiator ethylene glycol. Subsequently, the resulting PCL was converted to tetrafunctional macroinitiator by the esterification with 2,2-dichloro acetyl chloride (DCAC). The H-shaped block copolymer was then synthesized by the ATRP of styrene. The polymers were characterized by NMR and GPC. Linear first-order kinetics, linearly increasing molecular weight with conversion, and low polydispersities observed from the ATRP of St showed that the polymerization was well controlled. (PSt)₂-b-PCL-b-(PSt)₂ block copolymers with varying molecular weight and controllable composition were obtained.     

One‐step synthesis of star‐block copolymers via simultaneous free radical polymerization of styrene and ring opening polymerization of ε‐caprolacton using tetrafunctional iniferter

Star‐block copolymers comprised of poly(styrene) (S) core and four poly(ε‐caprolacton) (ε‐CL) arms were synthesized by the combination of free radical polymerization (FRP) of S and ring opening polymerization (ROP) of ε‐CL in one‐step in the presence of tetrafunctional ineferter. The block copolymers were characterized by ¹H‐NMR and FTIR spectroscopy, gel permeation chromatography (GPC), and fractional precipitation method. ¹H ‐NMR and FTIR spectroscopy and GPC studies of the obtained polymers indicate that star‐block copolymers easily formed as result of combination FRP and ROP in one‐step. The γ values (solvent/precipitant volume ratio) were observed between 1.04–2.72 (mL/mL) from fractional measurements. The results show that when the initial S feed increased, the molecular weights of the star‐block copolymers also increased and the polydispersities of the polymers decreased. M_w/M_n values of the products were measured between 1.4 and 2.86 from GPC. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hairy fluorescent nanoparticles from one‐pot click chemistry and atom transfer radical emulsion polymerization

Well‐defined hairy and crosslinked fluorescent nanoparticles with diameters in the range 70–220 nm were obtained from simultaneous copper‐catalyzed alkyne–azide cycloaddition (CuAAC) and atom transfer radical emulsion polymerization (ATREP) of a mixture of styrene, divinylbenzene, 4‐vinylbenzylazide and 7‐propinyloxycoumarin (Cr), using bromide‐terminated poly(ethylene glycol) (PEG) as macroinitiator, Tween‐20 as emulsifier, copper(I) bromide as catalyst and pentamethyldiethylenetriamine as ligand. The generation of biocompatible PEG brushes and the introduction of fluorescent functionalities as well as crosslinking of nanoparticles were realized in one step. In order to verify that functionalization and propagation of polymer chains could be realized in a controlled manner by one‐pot simultaneous ATREP and CuAAC, linear block copolymers of PEG and polystyrene (PS) with partially clicked pendent Cr groups (PEG‐b‐(PS‐c‐Cr)) were synthesized. All prepared PEG‐b‐(PS‐c‐Cr) copolymers had a controlled molecular weight and defined molecular structure. The hairy fluorescent nanoparticles exhibit a low cytotoxicity and could find applications in cell labeling. © 2013 Society of Chemical Industry     

A Synthetic Approach to Star‐Like Polymers of Styrene and Butyl Acrylate by Linking Reactions using Functionalized Methacrylates

Summary: Coupling reactions between terminal functionalized polymer chains were chosen for the synthesis of star‐like polymers consisting of polystyrene and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] arms. For the preparation of terminal functionalized polymer chains a side reaction of the 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) mediated free radical polymerization of methacrylates could be used successfully to convert TEMPO terminated polymers into end functionalized polymers. The number of functionalized monomer units attached to the polymer chain is directly related to the TEMPO concentration during this reaction. Different polystyrenes and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] block copolymers were functionalized with a variable number of epoxide and alcohol groups at the chain end. For the determination of the optimal reaction parameters for the coupling reactions between these polymer chains, epoxy functionalized polystyrenes were converted with hydroxy functionalized polystyrenes under basic and acidic conditions. By activation with sodium hydride or boron trifluoride star‐like polymers were synthesized under mild conditions. The transfer of the reaction conditions to coupling reactions between end functionalized polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] copolymers showed that star‐like polymers with more than 12 arms were formed using boron trifluoride as activating agent.

     

Solution properties of hyperbranched polymers and synthetic application for amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator

Hyperbranched polystyrenes (PS) were prepared by living radical photopolymerization of N,N‐diethyldithiocarbamoylmethylstyrene (DTCS) as an inimer under UV irradiation. Branched PS with an average chain length between branching points of four styrene units was also prepared by living radical copolymerization of DTCS with styrene. The ratio of radius of gyration to hydrodynamic radius R_G/R_H for these hyperbranched polymers was in the range 0.82–0.89 in toluene. The translational diffusion coefficient D(C) showed a constant value in the range of 0–14 × 10^?3 g ml^?1 in toluene. It was found from these dilute solution properties that hyperbranched PSs formed a unimolecular structure even in a good solvent because of their compact nature. These hyperbranched PSs exhibited large amounts of photofunctional carbamate (DC) groups on their outside surfaces. Subsequently, we derived amphiphilic star‐hyperbranched copolymers by grafting from hyperbranched macroinitiator with 1‐vinyl‐2‐pyrrolidinone. These star‐hyperbranched copolymers were soluble in water and methanol. © 2001 Society of Chemical Industry     

Well-defined second-order nonlinear optical polymers by controlled radical polymerization,via multifunctional macromolecular chain transfer agent: Design,synthesis, and characterizations

To address the issue of the aggregation in second-order nonlinear optical (NLO) polymers we developed an approach based on the synthesis of a multifunctional macromolecular chain transfer agent. The controlled monomer insertion polymerization into the main chain by a ‘reversible addition-fragmentation chain transfer’ (RAFT) mechanism allows the spatial arrangement of the NLO chromophores along the polymeric chain in order to obtain sequence-ordered polymers. In a first step, a novel trithiocarbonate based macroinitiator containing the disperse red 19 (DR19) units in the main chain was synthesized by polycondensation; in a second step, this polymeric precursor was applied to the synthesis of a sequentially ordered polymer by controlled insertion radical polymerization of styrene. Size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) data revealed that, (i) for the first time, polystyrenes (PS) bearing DR19 dyes covalently bounded were obtained, and (ii) both the insertion reaction and the length of the polystyrene segments were accurately controlled. Whatever the incorporated dye amount, all the copolymers were soluble in common solvents. Second-order optical nonlinearity in corona-poled thin films was evaluated, and second harmonic coefficients up to 80 pm/V were determined for loading ratio lower than 10 wt-% (DR19/PS). This approach opens up opportunities for the incorporation of more efficient chromophores even in apolar matrices.     

Z-RAFT star polymerization of styrene: Comprehensive characterization using size-exclusion chromatography

Reversible addition-fragmentation chain transfer (RAFT) polymerizations of styrene in bulk at 80 °C using tri-, tetra-, and hexafunctional trithiocarbonates, in which the active RAFT groups are linked to the core via the stabilizing Z-group, were studied in detail. These Z-RAFT star polymerizations of styrene showed excellent molecular weight control up to very high monomer conversions and star sizes of more than 200 kDa. The application of high pressure up to 2600 bar was found to significantly increase the relative amount of living star polymer. Not even at very high monomer conversions and for large star molecules, a shielding effect of growing arms hampering the RAFT process could be identified. Absolute molecular weights of star polymers using a conventionally calibrated SEC setup were determined with high precision by using a mixture of linear and star-shaped RAFT agents. When using phenylethyl as the leaving R-group, well-defined star polymers that perfectly match the theoretical predictions were formed. However, when using benzyl as the leaving group, a pronounced impact of monomer conversion on the star polymer topology was observed and pure star polymers with the expected number of arms could not be obtained.     

Preparation and ionic conductive properties of all‐solid polymer electrolytes based on multiarm star block polymers

A series of star block polymers with a hyperbranched core and 26 arms are successfully synthesized by atom transfer radical polymerization of styrene (St), and poly(ethylene glycol) methyl ether methacrylate from a hyperbranched polystyrene (HBPS) multifunctional initiator. All‐solid polymer electrolytes composed of these multiarm star polymers and lithium salts are prepared. The influences of polyoxyethylene (PEO) side‐chain length, PEO content, lithium salt concentration and type, and the structure of polymer on ionic conductivity are systematically investigated. The resulting polymer electrolyte with the longest PEO side chains exhibits the best ionic conductive properties. The maximum conductivity is 0.8 × 10^?4 S cm^?1 at 25°C with EO/Li = 30. All the prepared multiarm star block polymers possess good thermal stability. The mechanical property is greatly improved owing to the existence of polystyrene blocks in the multiarm star polymer molecules, and flexible films can be obtained by solution‐casting technique. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization

The novel trifunctional reversible addition-fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS₃) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (M_w/M_n ≤ 1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV-vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)₃ (PS-b-PNIPAAM)₃, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and ¹H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ in mixed solution (DMF/CH₃OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)₃ decreased with the increase of relative length of PS in the block copolymers.     

Synthesis and Characterization of Dendritic Star Poly(L-Lactide)s

Summary Dendritic star poly(L-lactide)s (PLLAs) were prepared by ring opening polymerization using a hyperbranched aliphatic polyester as the core. The stars were characterized by gel permeation chromatography (GPC) and nuclear magnetic resonance spectroscopy (NMR). The result shows the star PLLAs have narrow molecular weight distribution and the length of arms can be well controlled in terms of the molar ratios of L-lactide to the initiator. The structure and thermal properties of the star polymers were investigated by means of X-ray diffraction (XRD) and differential scanning calorimetry (DSC). XRD shows that the formation of star structure does not alter the structure of crystal of PLLA. The results of DSC indicate that the glass transition temperature (T_g) and the crystallinity of the star polymers increased with increasing the lengths of arms. It is identified that the crystallization of PLLA was effectively suppressed by the formation of star topology.     

Synthesis and characterization of four‐arm star‐shaped polymers and copolymers

Four‐arm star‐shaped polymers and copolymers were obtained by transition metal‐catalyzed atom‐transfer radical polymerization (ATRP). The polymers were characterized by FTIR and ¹H‐NMR spectroscopy. Gel permeation chromatography results indicated the formation of polystyrene and polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) arms with controlled molecular weights. In dilute solution, the linear polymers had higher inherent viscosities than star‐shaped ones. Thermogravimetric analysis showed a similar degradation mechanism for linear and star‐shaped polymers. Differential scanning calorimetry indicated the successful formation of diblock star‐shaped copolymers. Copyright © 2006 Society of Chemical Industry     

Synthesis and thermoresponsive properties of four arm, amphiphilic poly(tert-butyl-glycidylether)-block-polyglycidol stars

A series of four arm stars with copolymer arms composed of poly(tert-butyl-glycidylether)-b-polyglycidol were prepared using a multi-step process based on anionic ring-opening polymerization. Control of the length of the arms and the number of functional (hydroxyl) reactive groups was achieved by anionic polymerization. Stars with molar masses up to 12200 g/mol were prepared. The amphiphilic character of the star structure was varied using different polyglycidol block lengths. The star structure and molar mass of the obtained stars were characterized by SEC-MALLS and NMR spectroscopy.The temperature behavior of an aqueous solution of the obtained polymers was also investigated. The phase transition temperature was strongly dependent on the hydrophilic-hydrophobic balance of the star structure and varied in the range of 25-59 °C. As shown by DLS and SEM, the stars formed temperature-sensitive spherical aggregates in aqueous solution. The aggregates may be used for controlled transport and release of active compounds.     

Facile synthesis of multiblock copolymers composed of poly(tetramethylene oxide) and polystyrene using living free-radical polymerization macroinitiator

A facile synthetic strategy for well-defined multiblock copolymers utilizing ‘living’ free-radical polymerization macroinitiator has been presented. Polyurethane composed of alkoxyamine initiating units and poly(tetramethylene oxide) (PTMO) segments was prepared by polyaddition of tolylene 2,4-diisocyanate terminated PTMO with an alkoxyamine-based diol. Polymerization of styrene with the polyurethane macroinitiator was carried out under nitroxide-mediated free-radical polymerization (NMRP) condition. GPC, NMR, and IR data revealed that the polymerization was accurately controlled and well-defined polystyrene chains were inserted in the main chain of macroinitiator to give the poly(tetramethylene oxide)-b-polystyrene multiblock copolymers. The synthesized multiblock copolymers were characterized by tensile test, differential scanning calorimetry, and dynamic mechanical analysis. Mechanical properties of the multiblock copolymers can be tuned by the sufficient molecular weight control of PS chains. Soft segment of PTMO and hard segment of PS were apparently compatible due to the multiblock structure of low molecular weight segments and polar urethane groups.     

Design and synthesis of star polymers with hetero-arms by the combination of controlled radical polymerizations and click chemistry

An alternative approach to the synthesis of well-defined star polymers with hetero-arms was described. An azide-functionalized dithioester chain transfer agent (CTA-N₃) was designed and synthesized. Using CTA-N₃ as the reversible addition-fragmentation chain transfer (RAFT) agent, styrene was polymerized in a controlled manner. The so-obtained polystyrene showed a high proportion of azide-functionalized chains (PS-N₃, about 92%). The azide end-capped PS-N₃ could be assembled, via click reaction with a bromide-containing trialkyne coupling agent, to form a 3-arm star polystyrene (PS₃-Br) with a narrow molecular weight distribution. PS₃-Br could further serve as a macro-initiator for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Accordingly, well-defined star polymers containing three polystyrene and one poly(methyl methacrylate) (PMMA) arms, and with a narrow molecular weight distribution, were successfully prepared.     

Synthesis and characterization of polystyrene/poly(4‐vinylpyridine) triblock copolymers by reversible addition–fragmentation chain transfer polymerization and their self‐assembled aggregates in water

Reversible addition–fragmentation chain transfer polymerization (RAFT) was developed for the controlled preparation of polystyrene (PS)/poly(4‐vinylpyridine) (P4VP) triblock copolymers. First, PS and P4VP homopolymers were prepared using dibenzyl trithiocarbonate as the chain transfer agent (CTA). Then, PS‐b‐P4VP‐b‐PS and P4VP‐b‐PS‐b‐P4VP triblock copolymers were synthesized using as macro‐CTA the obtained homopolymers PS and P4VP, respectively. The synthesized polymers had relatively narrower molecular weight distributions (M_w/M_n < 1.25), and the polymerization was controlled/living. Furthermore, the polymerization rate appeared to be lower when styrene was polymerized using P4VP as the macro‐CTA, compared with polymerizing 4‐vinylpyridine using PS as the macro‐CTA. This was attributed to the different transfer constants of the P4VP and PS macro‐CTAs to the styrene and the 4‐vinylpyridine, respectively. The aggregates of the triblock copolymers with different compositions and chain architectures in water also were investigated, and the results are presented. Reducing the P4VP block length and keeping the PS block constant favored the formation of rod aggregates. Moreover, the chain architecture in which the P4VP block was in the middle of the copolymer chain was rather favorable to the rod assembly because of the entropic penalty associated with the looping of the middle‐block P4VP to form the aggregate corona and tailing of the end‐block PS into the core of the aggregates. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1017–1025, 2003