Swelling behavior of ordered miktoarm star block copolymer-homopolymer blends

We report the morphological characterization of asymmetric miktoarm star block copolymers of the (PS-b-PI)_nPS type where n=2,3 (denoted 2DB and 3DB miktoarm stars, respectively) and a symmetric super H-shaped block copolymer of the (PS-b-PI)₃PS(PI-b-PS)₃ type (denoted SH) which were synthesized by anionic polymerization. The initial volume fraction of PS (φ_PS) for each copolymer was 0.51-0.56, giving a lamellar morphology. Addition of homopolystyrene (hPS) with a molecular weight lower than the respective PS blocks in the neat materials lead to a transition from the lamellar structure to hexagonally packed cylinders. Addition of low molecular weight homopolyisoprene (hPI) on the other hand, only resulted in swollen lamellae even when the overall composition was highly asymmetric (80/20). Changes in the lamellar spacing as well as in the respective PS and PI layer thickness were measured by SAXS. The transition from lamellae to cylinders with increased PS content occurred without the observation of an intervening cubic morphology for the 2DB and 3DB miktoarm stars. However, blends with 30 and 35% hPS ((φ_PS)_total=0.68-0.70) with the super H-shaped block copolymer lead to the observation of lamellar-catenoid structures.     

Synthesis of Y‐shaped poly(N,N‐dimethylamino‐2‐ethyl methacrylate) and poly(trimethylene carbonate) from a new heterofunctional initiator

A new amphiphilic Y‐shaped copolymer, comprised of hydrophobic Poly(trimethylene carbonate) (PTMC) and hydrophilic Poly(N,N‐dimethylamino‐2‐ethyl methacrylate) (PDMAEMA), was designed and synthesized by a combination of atom transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP) using a new heterofunctional initiator, Br‐Init‐(OH)₂, bearing one initiation site for ATRP and two for ROP. At first, a new trifunctional core molecule bearing hydroxyl group and bromine moieties, Br‐Init‐(OH)₂, was synthesized via protection followed by esterification reaction of 5‐ethyl‐5‐hydroxymethyl‐2,2‐dimethyl‐1,3‐dioxane with 2‐bromoisobutyryl bromide and deprotection. In the presence of trifunctional core molecule, Br‐Init‐(OH)₂, target Y‐shaped miktoarm star copolymers, (PTMC)₂‐ b‐PDMAEMA, were successfully synthesized by sequence conducting the ROP of TMC and ATRP of DMAEMA. The Y‐shaped copolymers were characterized by ¹H NMR and GPC measurements. Subsequently, the self‐assembly behavior of these copolymers was investigated by dynamic light scattering method and transmission electron microscopy, which indicated that these amphiphilic Y‐shaped copolymers can self‐assemble into micelles and possess distinct pH‐dependent size in aqueous milieu. The results indicate that the amphiphilic Y‐shaped copolymers had the pH‐responsive properties similar to the expected PDMAEMA. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

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 of A<Subscript>2</Subscript>B<Subscript>2</Subscript> miktoarm star copolymers from a new heterobifunctional initiator by combination of ROP and ATRP

Abstract  

A new heterobifunctional initiator, 2,3-bis(2-bromo-2-methylpropionyloxy) succinic acid, was synthesized and used in preparation of A₂B₂ miktoarm star copolymers, (polystyrene)₂(poly(ε-caprolactone))₂, by combination of atom transfer radical polymerization (ATRP) and Controlled ring-opening polymerization (ROP). The structures of products were confirmed by the ¹H NMR, ¹³C NMR, FT–IR, elemental analysis, differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). GPC traces show that the obtained polymers have a relatively narrow molecular weight distribution. The compositions of resulting miktoarm star copolymers were very close to theoretical.     

Synthesis of a Novel Miktoarm Star Azobenzene Side-Chain Liquid Crystalline Copolymers by Atom Transfer Radical Polymerization

Summary A series of miktoarm star novel azobenzene side-chain liquid crystalline (LC) copolymers were synthesized by combination of atom transfer radical polymerization (ATRP) and chemical modification of the termini of ATRP-derived polymers. These miktoarm star copolymers carrying one polystyrene (PS) arm and two poly [6-(4-methoxy-4-oxy-azobenzene) hexylmethacrylate] (PMMAZO) arms were characterized by ¹H NMR and GPC. The liquid crystailline behavior of these copolymers was studied by DSC and POM. It was found that the miktoarm star copolymers have the similar LC properties to PMMAZO homopolymer, and their thermal stability of the mesophases is increased, while the phase transition enthalpies are reduced.     

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).     

Preparation and properties of azobenzene-containing amphiphilic miktoarm star polymers

Summary A series of novel miktoarm star polymers composed of a poly(ethylene oxide) (PEO) and two side-chain liquid crystalline azobenzene-containing polymethacrylate (PEO-(PMMAZO)₂) were prepared using atom transfer radical polymerization (ATRP). Bifunctional macroinitiator PEO-Br₂ was synthesized by condensation reaction in two steps and characterized by ¹H NMR, ¹³C NMR and IR. Kinetic study showed that it was a first order reaction referred to the monomer MMAZO, namely, 6-(4-methoxy-4’-oxy-azobenzene)hexyl methacrylate. The liquid crystalline behaviors of the miktoarm star polymers were studied by differential scanning calorimetry (DSC) and polarized optical microscope (POM). They exhibited smectic and nematic mesophases when Mn was beyond 9.4×10³ g/mol. The phase transition temperatures of the smectic and nematic phases increased while the melting temperature of PEO decreased with increasing molecular weight of the LC block. Compared with diblock polymer PEO-PMMAZO, the melting temperature of PEO in miktoarm star polymer decreased more rapidly.     

Synthesis and characterization of a novel liquid crystalline star‐shaped polymer based on α‐CD core via ATRP

Well‐defined side‐chain liquid crystalline star‐shaped polymers were synthesized with a combination of the “core‐first” method and atom transfer radical polymerization (ATRP). Firstly, the functionalized macroinitiator based on the α‐Cyclodextrins (α‐CD) bearing functional bromide groups was synthesized, confirmed by ¹H‐NMR, MALDI‐TOF, and FTIR analysis. Secondly, the side‐chain liquid crystalline arms poly[6‐(4‐methoxy‐4‐oxy‐azobenzene) hexyl methacrylate] (PMMAzo) were prepared by ATRP. The characterization of the star polymers were performed with ¹H‐NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermal polarized optical microscopy (POM). It was found that the liquid crystalline behavior of the star polymer α‐CD‐PMMAzo_n was similar to that of the linear homopolymer. The phase‐transition temperatures from the smectic to nematic phase and from the nematic to isotropic phase increased as the molecular weight increased for most of these samples. All star‐shaped polymers show photoresponsive isomerization under the irradiation with Ultraviolet light. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and self-assembly of miktoarm star copolymers of (polyethylene)2−(polystyrene)2

We report on the synthesis and self-assembly of a novel well-defined miktoarm star copolymer of (polyethylene)₂−(polystyrene)₂, (PE)₂−(PS)₂, with two linear crystalline PE segments and two PS segments as the building blocks based on chain shuttling ethylene polymerization (CSEP), click reaction and atom transfer radical polymerization (ATRP). Initially, alkynyl-terminated PE (PE-) was synthesized via the esterification of pentynoic acid with hydroxyl-terminated PE (PE−OH), which was prepared using CSEP with 2,6-bis[1-(2,6-dimethylphenyl) imino ethyl] pyridine iron (II) dichloride/methylaluminoxane/diethyl zinc and subsequent in situ oxidation with oxygen. (PE)₂−(OH)₂ was then obtained by the click reaction of PE- with diazido and dihydroxyl containing coupling agent. The two hydroxyl groups in (PE)₂−(OH)₂ were then converted into bromisobutyrate by esterification. At last, the (PE)₂−(PS)₂ miktoarm star copolymers were synthesized by ATRP of styrene initiated from (PE)₂−Br₂ macroinitiator. All the intermediates and final products were characterized by ¹H NMR and gel permeation chromatography (GPC). The self-assembly behavior was studied by dynamic light scattering (DLS) and atomic force microscopy (AFM). The crystallization of the (PE)₂−(PS)₂ miktoarm star copolymers was studied by differential scanning calorimetry (DSC).     

Effect of molecular architecture on the self-diffusion of polymers in aqueous systems: A comparison of linear, star, and dendritic poly(ethylene glycol)s

Star polymers with a hydrophobic cholane core and four poly(ethylene glycol) (PEG) arms, CA(EG_n)₄, have been synthesized by anionic polymerization. Pulsed-gradient spin-echo NMR spectroscopy was used to study the diffusion behavior of the star polymers, ranging from 1000 to 10,000 g/mol, in aqueous solutions and gels of poly(vinyl alcohol) (PVA) at 23 °C. The star polymers have a lower self-diffusion coefficient than linear PEGs at equivalent hydrodynamic radius. In water alone, the star polymers and their linear homologues have a similar diffusion behavior in the dilute regime, as demonstrated by the similar concentration dependence of the self-diffusion coefficients. In the semidilute regime, the star polymers tend to aggregate due to their amphiphilic properties, resulting in lower self-diffusion coefficients than those of linear PEGs. ¹H NMR T₁ measurements at 10-70 °C revealed that the PEG arms of the star polymers are more mobile than the core, suggesting the star polymers in solution have a conformation similar to that of poly(propylene imine) dendrimers.     

A new approach to 3-miktoarm star polymers using a combination of reversible addition-fragmentation chain transfer (RAFT) and ring opening polymerization (ROP) via “Click” chemistry

The synthesis of AB₂-type miktoarm star polymers using a combination of reversible addition-fragmentation chain transfer (RAFT), ring opening polymerization (ROP) and “Click” chemistry was demonstrated in this work. An azide functional RAFT agent was used to polymerize butyl acrylate, polyethylene glycol acrylate and N-isopropylacrylamide monomers. Propargylamine was reacted with glycerine carbonate to obtain a dihydroxy functional alkyne compound which was used for the ring opening polymerization of ?-caprolactone (?-CL) and lactide. The resulting alkyne functional polycaprolactone (PCL) and polylactide (PLA) polymers were reacted with azide functional polymers in the presence of copper bromide (CuBr) catalyst to obtain miktoarm star polymers. The polymers were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. The star polymers had low polydispersity (∼1.3) with well-defined structures. These polymers have a number of potential applications including crosslinking agents for polyurethane (PU) coatings for biodegradable and fouling release applications.     

Preparation of star polymers of hyperbranched polyglycerol core with multiarms of PS‐b‐PtBA and PS‐b‐PAA

Atom transfer radical polymerization (ATRP) was applied to synthesize a new kind of star polymers of hyperbranched polyglycerol (HPG) core with multiarms of PS‐b‐PtBA and PS‐b‐PAA by using the “core first” technique. The HPG core was obtained by anionic polymerization of glycerol first, and then the pendant hydroxyl groups of HPG were esterified with 2‐bromoisobutyryl bromide to yield the HPG‐g‐Br, which was used as macroinitiator for ATRP of the first monomer (St) and then second monomer (tBA). After hydrolysis of the PtBA block, poly(acrylic acid) (PAA) side chains were formed. The final products and intermediates were characterized by GPC, NMR, and FTIR in detail. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New main-chain hyperbranched polymers: Facile synthesis,structural control,and second-order nonlinear optical properties

In this paper, two new series of hyperbranched main-chain polymers, P1–P6, with chromophore moieties as the core were successfully prepared through “A₃+B₂” approach via simple Sonogashira coupling reaction. By changing the bulky size of comonomers, the structure-property relationship has been investigated according to the concept of “suitable isolation group”. The second harmonic generation (SHG) experiments demonstrated that the hyperbranched structure might be very good architecture for the development of NLO materials with high performance. The benzene ring (Bz) could act as suitable isolation groups in these polymers, while the d₃₃ values of the corresponding polymers P1 and P4, were 152.6 and 86.2 pm/V, respectively, much higher than their linear analog polymers bearing the same chromophore moieties. In addition, these hyperbranched main-chain polymers could combine the large nonlinearities of hyperbranched polymers and high stability of main-chain polymers, providing a new solution to solve the “nonlinearity-stability” trade off existing in the main-chain polymers to some degree.     

A novel amphiphilic AB2 star copolymer synthesized by the combination of ring-opening metathesis polymerization and atom transfer radical polymerization

A new amphiphilic AB₂ star copolymer was synthesized by the combination of ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP). Two different routes (methods A and B) were employed firstly to prepare the poly(oxanorbornene)-based monotelechelic polymers as the hydrophobic arm bearing dibromo-ended group via ROMP in the presence of two different terminating agents catalyzed by first generation Grubbs catalyst. The values of capping efficiency (CE) of the polymers were determined by NMR, which were 94% and 67% for methods A and B, respectively. Then, the dibromo-ended ROMP polymers were used as the macroinitiators for ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA) to produce two hydrophilic arms. The prepared amphiphilic AB₂ star copolymers poly(7-oxanorborn-5-ene-exo,exo-2,3-dicarboxylic acid dimethyl ester)-block-bis[poly(2-(dimethylamino)ethyl methacrylate)] (PONBDM_n-b-(PDMAEMA_m)₂) with a fixed chain length of hydrophobic PONBDM and various hydrophilic PDMAEMA chain lengths can self-assemble spontaneously in water to form polymeric micelles, which were characterized by dynamic light scattering, atom force microscopy, and transmission electron microscopy measurements.     

Star-shaped condensation polymers: Synthesis,characterization, and blend properties

A series of ?-caprolactone linear and star polymers were prepared and characterized in order to determine the effect of the star architecture (i.e., star number and arm length) on the morphology of these semicrystalline polymers. A spherulitic morphology was found in all the polymers investigated. However, for six arm stars containing low degrees of polymerization, it appears that the star core dominates its morphological behavior (presumably due to its relatively high volume fraction). The star core effects, however, are markedly reduced in star polymers were the arms contain higher degrees of polymerization. The impact of the star core was further explored by investigating several poly(?-caprolactone) (PCL):styrene–acrylontrile copolymers (SAN) blends. In all instances, miscible blends were the result because a single compositionally dependent glass-transition temperature (T_g) was observed. A moderate elevation in the T_g of the star-shaped polymers does occur, however, compared to their linear analogs. This effect is presumably due to the inability of the SAN chains to completely mix with all segments of star structure. © 1993 John Wiley & Sons, Inc.     

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.     

Copper nanowire/PA6 composites prepared by in situ polymerization and its properties

Most magnetic composite materials have a serious sedimentation problem because of their large density. When the nanomaterials are combined with magnetic materials, the density would become larger. In this article, polystyrene (PS) beads were used as core to synthesize raspberry-like PS-Fe₃O₄@TiO₂ particles (PFTPs) by a facile method, which could float on the water. The loaded Fe₃O₄@TiO₂ particles were characterized by X-ray diffraction (XRD), which could confirm the anatase phase TiO₂ coated on Fe₃O₄ nano-particles. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) confirmed the presence of acrylic acid in reaction media could effectively tune the morphology of resulting composite particles between “core-shell” and “raspberry-like”. The data of Vibrating sample magnetometer (VSM) indicated the change in saturation magnetization before and after TiO₂ coated, the introduction of PS could further influence the saturation magnetization of Fe₃O₄. Lastly, we proved the sedimentation stability of PFTPs via capturing the photographs of them in water and oil.     

Convenient syntheses of fullerynes for ‘clicking’ into fullerene polymers

Alkyne-functionalized fullerenes (fullerynes) were designed and conveniently synthesized via Bingel reaction in one step with high yields. They were used to react with azido-functionalized polystyrene (PS) via Huisgen [3 + 2] cycloaddition ‘click’ chemistry to form two fullerene polymers: one with C₆₀ tethered to the end of a PS chain (C₆₀-1PS) and the other with C₆₀ tethered at the junction point of two PS chains of identical molecular weight (C₆₀-2PS). The fullerene polymers were characterized by ¹H NMR, ¹³C NMR, FT-IR, MALDI-TOF mass spectrometry and SEC. The results showed that the fullerene polymers are well-defined with narrow polydispersity and high fullerene functionality. Besides, aggregation of C₆₀ in THF was observed in the SEC traces. The optical properties of the fullerene polymers were studied by UV–Vis absorption spectroscopy, and the results suggested that the PS chain(s) on the fullerene core has no remarkable effect on the optic property of C₆₀. The thermal properties of the fullerene polymers were studied by TGA and DSC, and the results indicated that the two fullerene polymers with different C₆₀ content and distinct molecular topology may have different self-assemble architectures in the solid state. The well-defined fullerene polymers can be used as model compounds to study the self-assemble architecture of shape amphiphiles based on polymer-tethered molecular nanoparticles.     

Mechanism for the formation of PNIPAM/PS core/shell particles

A multi‐stage polymerization method was previously used to prepare PNIPAM/PS core/shell particles that exhibited uniform “raspberry‐like” structures. In this current study, this polymerization process was carefully investigated in order to elucidate the PS (polystyrene) shell formation mechanism. The results indicated that the “raspberry” structure is due to heterocoagulation of polystyrene domains onto PNIPAM (poly(N‐isopropylacrylamide)) particle surfaces. Different sizes and numbers of the PS domains can be obtained by varying the styrene feed rate. It was also found that linear PNIPAM may increase the compatibility between PNIPAM and PS polymers. In addition, this heterocoagulation mechanism for forming structured particles was successfully applied to a PNIPAM and Ludox^® colloidal silica nanoparticle system where a core/shell structure was also obtained. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40124.