Amphiphilic comb-like pentablock copolymers of Pluronic L64 and poly(ethylene glycol)methyl ether methacrylate: synthesis by ATRP,self-assembly,and clouding behavior

Well-defined amphiphilic comb-like pentablock copolymers based on Pluronic L64 (PEO₁₃-b-PPO₃₀-b-PEO₁₃) and poly(ethylene glycol)methyl ether methacrylate (PEGMA) have been successfully synthesized via atom transfer radical polymerization (ATRP). The L64 is transformed into ATRP macroinitiator and chain extended with PEGMA under typical ATRP conditions to achieve comb-like pentablock copolymers of various compositions. Due to their amphiphilic nature, the block copolymers could form self-assembled structures in aqueous solutions as confirmed by dynamic light scattering. At higher PEGMA content in the synthesized copolymer, however, the critical aggregation concentration (CAC) is less pronounced that could be attributed to the increased hydrophilicity and steric hindrance of PEG side chains of the PEGMA, thus preventing the formation of well-defined micellar aggregates, and probably leads to open-shell aggregation mechanism. The lower critical solution temperature (LCST) of the synthesized block copolymers is found higher than the neat L64 and increased with increasing the PEGMA content. Further, tuning the clouding behavior could be achieved with inorganic additives (KBr and K₂SO₄). The influence of SO₄^2? and Br^1? on LCST is according to their position in Hofmeister series. Interestingly, the effect of additives is more pronounced above the CAC of the copolymer, suggesting that the nanoaggregates in solution induce the macrophase separation.     

Synthesis and characterization of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers with dibutylmagnesium as catalyst

Two series of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) triblock copolymers were prepared by the ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) and dibutylmagnesium in 1,4‐dioxane solution at 70°C. The triblock structure and molecular weight of the copolymers were analyzed and confirmed by ¹H NMR, ¹³C NMR, FTIR, and gel permeation chromatography. The crystallization and thermal properties of the copolymers were investigated by wide‐angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC). The results illustrated that the crystallization and melting behaviors of the copolymers were depended on the copolymer composition and the relative length of each block in copolymers. Crystallization exothermal peaks (T_c) and melting endothermic peaks (T_m) of PEG block were significantly influenced by the relative length of PCL blocks, due to the hindrance of the lateral PCL blocks. With increasing of the length of PCL blocks, the diffraction and the melting peak of PEG block disappeared gradually in the WAXD patterns and DSC curves, respectively. In contrast, the crystallization of PCL blocks was not suppressed by the middle PEG block. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of biodegradable polymers composed of 3,4-dihydroxycinnamic acid and poly(ethylene glycol)

A novel series of biodegradable copolymers were synthesized by the thermal polycondensation of 3,4-dihydroxycinnamic acid (DHCA) and poly(ethylene glycol) (PEG). The copolymers were characterized by ¹H-NMR, Fourier transform infrared spectroscopy, and gel permeation chromatography. It was found that the incorporation of PEG reduced the glass-transition temperature (T_g) of the copolymers, and T_g decreased with increasing amount of PEG in the compositions. The fluorescence spectroscopy revealed that the homopolymer and copolymers of DHCA gave a higher fluorescence emission intensity than that of DHCA monomer, of which the strongest fluorescence emission peak occurred in the copolymers containing a small amount of PEG. X-ray diffraction spectra demonstrated that poly(3,4-dihydroxycinnamic acid) and copolymer were amorphous; this indicated the facile biodegradability of the copolymers. Furthermore, copolymer micelles formed by self-assembly were investigated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Comparison of micelles formed by amphiphilic poly(ethylene glycol)‐b‐poly(trimethylene carbonate) star block copolymers

In this article, we describe the synthesis and solution properties of PEG‐b‐PTMC star block copolymers via ring‐opening polymerization (ROP) of trimethylene carbonate (TMC) monomer initiated at the hydroxyl end group of the core PEG using HCl Et₂O as a monomer activator. The ROP of TMC was performed to synthesize PEG‐b‐PTMC star block copolymers with one, two, four, and eight arms. The PEG‐b‐PTMC star block copolymers with same ratio of between hydrophobic PTMC and hydrophilic PEG segments were obtained in quantitative yield and exhibited monomodal GPC curves. The amphiphilic PEG‐b‐PTMC star block copolymers formed spherical micelles with a core–shell structure in an aqueous phase. The mean hydrodynamic diameters of the micelles increased from 17 to 194 nm with increasing arm number. As arm number increased, the critical micelle concentration (CMC) of the PEG‐b‐PTMC star block copolymers increased from 3.1 × 10^?3 to 21.1 × 10^?3 mg/mL but the partition equilibrium constant, which is an indicator of the hydrophobicity of the micelles of the PEG‐b‐PTMC star block copolymers in aqueous media, decreased from 4.44 × 10⁴ to 1.34 × 10⁴. In conclusion, we confirmed that the PEG‐b‐PTMC star block copolymers form micelles and, hence, may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The role of the ratio (PEG:PPG) of a triblock copolymer (PPG‐b‐PEG‐b‐PPG) in the cure kinetics,miscibility and thermal and mechanical properties in an epoxy matrix

The aim of this study was to evaluate the role of different poly(ethylene glycol):poly(propylene glycol) (PEG:PPG) molar ratios in a triblock copolymer in the cure kinetics, miscibility and thermal and mechanical properties in an epoxy matrix. The poly(propylene glycol)‐block‐poly(ethylene glycol)‐block‐poly(propylene glycol) (PPG‐b‐PEG‐b‐PPG) triblock copolymers used had two different molecular masses: 3300 and 2000 g mol^?1. The mass concentration of PEG in the copolymer structure played a key role in the miscibility and cure kinetics of the blend as well as in the thermal–mechanical properties. Phase separation was observed only for blends formed with the 3300 g mol^?1 triblock copolymer at 20 wt%. Concerning thermal properties, the miscibility of the copolymer in the epoxy matrix reduced the T_g value by 13 °C, although a 62% increase in fracture toughness (K_IC) was observed. After the addition of PPG‐b‐PEG‐b‐PPG with 3300 g mol^?1 there was a reduction in the modulus of elasticity by 8% compared to the neat matrix; no significant changes were observed in T_g values for the immiscible system. The use of PPG‐b‐PEG‐b‐PPG with 2000 g mol^?1 reduced the modulus of elasticity by approximately 47% and increased toughness (K_IC) up to 43%. Finally, for the curing kinetics of all materials, the incorporation of the triblock copolymer PPG‐b‐PEG‐b‐PPG delayed the cure reaction of the DGEBA/DDM (DGEBA, diglycidyl ether of bisphenol A; DDM, Q3‐4,4′‐Diaminodiphenylmethane) system when there is miscibility and accelerated the cure reaction when it is immiscible. All experimental curing reactions could be fitted to the Kamal autocatalytic model presenting an excellent agreement with experimental data. This model was able to capture some interesting features of the addition of triblock copolymers in an epoxy resin. © 2018 Society of Chemical Industry     

Influence of the synthesis conditions on the structural and thermal properties of poly(l‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l‐lactide)

The poly(l ‐lactide)‐b‐poly(ethylene glycol)‐b‐poly(l ‐lactide) block copolymers (PLLA‐b‐PEG‐b‐PLLA) were synthesized in a toluene solution by the ring‐opening polymerization of 3,6‐dimethyl‐1,4‐dioxan‐2,5‐dione (LLA) with PEG as a macroinitiator or by transterification from the homopolymers [polylactide and PEG]. Two polymerization conditions were adopted: method A, which used an equimolar catalyst/initiator molar ratio (1–5 wt %), and method B, which used a catalyst content commonly reported in the literature (<0.05 wt %). Method A was more efficient in producing copolymers with a higher yield and monomer conversion, whereas method B resulted in a mixture of the copolymer and homopolymers. The copolymers achieved high molar masses and even presenting similar global compositions, the molar mass distribution and thermal properties depends on the polymerization method. For instance, the suppression of the PEG block crystallization was more noticeable for copolymer A. An experimental design was used to qualify the influence of the catalyst and homopolymer amounts on the transreactions. The catalyst concentration was shown to be the most important factor. Therefore, the effectiveness of method A to produce copolymers was partly due to the transreactions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40419.     

Synthesis and characterization of temperature‐sensitive block copolymers from poly(N‐isopropylacrylamide) and 4‐methyl‐ε‐caprolactone or 4‐phenyl‐ε‐caprolactone

This study synthesizes thermally sensitive block copolymers poly(N‐isopropylacrylamide)‐b‐poly(4‐methyl‐ε‐caprolactone) (PNIPA‐b‐PMCL) and poly(N‐isopropylacrylamide)‐b‐poly(4‐phenyl‐ε‐caprolactone) (PNIPA‐b‐PBCL) by ring‐opening polymerization of 4‐methyl‐ε‐caprolactone (MCL) or 4‐phenyl‐ε‐caprolactone (BCL) initiated from hydroxy‐terminated poly(N‐isopropylacrylamide) (PNIPA) as the macroinitiator in the presence of SnOct₂ as the catalyst. This research prepares a PNIPA bearing a single terminal hydroxyl group by telomerization using 2‐hydroxyethanethiol (ME) as a chain‐transfer agent. These copolymers are characterized by differential scanning calorimetry (DSC), ¹H‐NMR, FTIR, and gel permeation chromatography (GPC). The thermal properties (T_g) of diblock copolymers depend on polymer compositions. Incorporating larger amount of MCL or BCL into the macromolecular backbone decreases T_g. Their solutions show transparent below a lower critical solution temperature (LCST) and opaque above the LCST. LCST values for the PNIPA‐b‐PMCL aqueous solution were observed to shift to lower temperature than that for PNIPA homopolymers. This work investigates their micellar characteristics in the aqueous phase by fluorescence spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS). The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (CMCs) in the range of 0.29–2.74 mg L^?1, depending on polymer compositions, which dramatically affect micelle shape. Drug entrapment efficiency and drug loading content of micelles depend on block polymer compositions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A biodegradable triblock copolymer poly(ethylene glycol)-b-poly(l-lactide)-b-poly(l-lysine): Synthesis,self-assembly,and RGD peptide modification

A novel biodegradable triblock copolymer poly(ethylene glycol)-b-poly(l-lactide)-b-poly(l-lysine) (PEG–PLA–PLL) was synthesized by acidolysis of poly(ethylene glycol)-b-poly(l-lactide)-b-poly(ɛ-benzyloxycarbonyl-l-lysine) (PEG–PLA–PZLL) obtained by the ring-opening polymerization (ROP) of ɛ-benzyloxycarbonyl-l-lysine N-carboxyanhydride (ZLys NCA) with amino-terminated PEG–PLA–NH₂ as a macroinitiator, and the pendant amino groups of the lysine residues were modified with a peptide known to modulate cellular functions, Gly-Arg-Gly-Asp-Ser-Tyr (GRGDSY, abbreviated as RGD) in the presence of 1,1′-carbonyldiimidazole (CDI). The structures of PEG–PLA–PLL/RGD and its precursors were confirmed by ¹H NMR, FT-IR, amino acid analysis and XPS analysis. The cell adhesion and cell spread on the PEG–PLA–PLL/RGD film were enhanced compared to those on pure PLA film. Therefore, the novel RGD-grafted triblock copolymer is promising for cell or tissue engineering applications. Both copolymers PEG–PLA–PZLL and PEG–PLA–PLL showed an amphiphilic nature and could self-assemble into micelles of homogeneous spherical morphology. The micelles were determined by fluorescence technique, dynamic light scattering (DLS), and field emission scanning electron microscopy (ESEM) and could be expected to find application in drug and gene delivery systems.     

Improving the antifouling properties of polypropylene surfaces by melt blending with polyethylene glycol diblock copolymers

Protein‐resistant polyethylene‐block‐poly(ethylene glycol) (PE‐b‐PEG) copolymers of different molecular weights at various concentrations were compounded by melt blending with polypropylene (PP) polymers in order to enhance their antifouling properties. Phase separation of the PE‐b‐PEG copolymer and its migration to the surface of the PP blend, was confirmed by attenuated total reflectance–Fourier transform infrared, X‐ray photoelectron spectroscopy, and static water contact angle measurements. Enrichment of PEG chains at the surface of the blends increased with increasing PE‐b‐PEG copolymer concentration and molecular weight. The PP blends compounded with PE‐b‐PEG copolymer having the lowest molecular weight (875 g mol^?1), at the lowest concentration (1 wt %), gave the lowest bovine serum protein adsorption (30% less) compared to that of neat PP. At higher concentrations (5 and 10 wt %), and higher molecular weights (920, 1400, and 2250 g mol^?1), the PE‐b‐PEG copolymers leached‐out resulting in protein adsorption comparable to that of neat PP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46122.     

Water soluble copolymers. 54: N-isopropylacrylamide-co-acrylamide copolymers in drag reduction: Synthesis,characterization, and dilute solution behavior

Copolymers of N-isopropylacrylamide (IPAM) and acrylamide (AM) have been synthesized by free radical polymerization in deionized water using potassium persulfate as the initiator. Copolymer compositions were obtained by elemental analysis and ¹³C NMR. An r₁r₂ value of 0.99 indicates ideal copolymerization with random incorporation of the comonomers in the copolymers. Weight average molecular weights, second virial coefficients, diffusion coefficients, and average diameters were obtained via classical and quasielastic low angle laser light scattering. The molecular weights for all the copolymers and the homopolymers of IPAM and AM ranged from 2.2 × 10⁶ to 5.2 × 10⁶ g/mol. The second virial coefficients in deionized water increased with increasing acrylamide content in the copolymers. The dilute solution properties of the copolymers were studied by turbidimetry, microcalorimetry and viscometry. All the copolymers, with the exception of IPAM-40 (the copolymer synthesized with 40 mole% IPAM in the feed), showed lower critical solution temperatures below 100°C. The solution studies were performed in deionized water, 0.514 M NaCl, and 1 M urea. The properties of the IPAM copolymers were influenced by both hydrophobic associations and hydrogen bonding. In 0.2% (～7mM) sodium dodecyl sulfate, the alkyl chain of the surfactant molecules associates with the IPAM moieties on the copolymer backbone, leading to high intrinsic viscosities and the elevation of the LCST above 100°C.     

Synthesis and self‐assembly of amphiphilic star‐block copolymers consisting of polyethylene and poly(ethylene glycol) segments

We report on the synthesis and self‐assembly in water of well‐defined amphiphilic star‐block copolymers with a linear crystalline polyethylene (PE) segment and two or three poly(ethylene glycol) (PEG) segments as the building blocks. Initially, alkynyl‐terminated PE (PE‐?) is synthesized via esterification of pentynoic acid with hydroxyl‐terminated PE, which is prepared using chain shuttling ethylene polymerization with 2,6‐bis[1‐(2,6‐dimethylphenyl) imino ethyl] pyridine iron (II) dichloride/methylaluminoxane/diethyl zinc and subsequent in situ oxidation with oxygen. Then diazido‐ and triazido‐terminated PE (PE‐(N₃)₂ and PE‐(N₃)₃) are obtained by the click reactions between PE‐? and coupling agents containing triazido or tetraazido, respectively. Finally, the three‐arm and four‐arm star‐block copolymers, PE‐b‐(PEG)₂ and PE‐b‐(PEG)₃, are prepared by click reactions between PE‐(N₃)₂ or PE‐(N₃)₃ and alkynyl‐terminated PEG. The self‐assembly of the resultant amphiphilic star‐block copolymers in water was investigated by dynamic light scattering, transmission electron microscopy, and atomic force microscopy. It is found that, in water, a solvent selectively good for PEG blocks; these star‐block copolymer chains could self‐assemble to form platelet‐like micelles with insoluble PE blocks as crystalline core and soluble PEG blocks as shell. The confined crystallization of PE blocks in self‐assembled structure formed in aqueous solution is investigated by differential scanning calorimetry. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermoresponsive core-shell-corona micelles of poly(ethyleneglycol)-b-poly(N-isopropylacrylamide)-b-polystyrene

Core-shell-corona micelles with a thermoresponsive shell self-assembled by triblock copolymer of poly(ethyleneglycol)-b-poly(N-isopropylacrylamide)-b-polystyrene (PEG₄₅-b-PNIPAM₁₆₈-b-PS₄₆) are studied by ¹H NMR, light scattering and atomic force microscopy. The thermoresponsive triblock copolymer, which has a relatively short hydrophobic PS block, can disperse in water at room temperature to form core-shell-corona micelles with the hydrophobic PS block as core, the thermoresponsive PNIPAM block as shell and the hydrophilic PEG block as corona. At temperature above lower critical solution temperature (LCST) of the PNIPAM block, the PNIPAM chains gradually collapse on the PS core to shrink the size and change the structure of the resultant core-shell-corona micelles with temperature increasing. It is found that there possibly exists an interface between the PNIPAM shell and PEG corona of the core-shell-corona micelles at temperature above LCST of the PNIPAM block.     

Synthesis,characterization and micellization of heterograft copolymers based on phosphoester functionalized macromonomers via “grafting through” method

Novel amphiphilic heterograft copolymers consisting of phosphoester functionalized PEG (phosPEG) and PCL (phosPCL) were synthesized by the ring‐opening polymerization via “grafting through” method. The heterograft structure and thermal properties of these copolymers with various compositions were characterized by ¹H‐NMR, ³¹P NMR, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) in detail. These amphiphilic copolymers could self‐assemble into micellar structures in aqueous solution, and their critical micellization concentrations (CMC) were determined to be 0.69–1.25 mg/L by fluorescence technique. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) measurements show that these heterograft copolymer micelles are spherical in shape with the particle size ranging from 20 to 60 nm, which has potential in biomedical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of novel twin‐tailed hydrophobically associated copolymers and their applications to Cr(III) removal from aqueous solutions

Water pollution is one of the most serious environmental problems facing society. The objective of this study was to provide an efficient and inexpensive way of removing Cr(III) from polluted water. Novel twin‐tailed hydrophobically associating copolymers (PAAD) were prepared by micellar copolymerization of acrylamide (AM) and sodium 2‐acrylamido‐2‐methylpropane sulfonate with N,N‐dibutylmethacrylamide in an aqueous solution. The PAAD series, comprising copolymers of different molecular weights (ranged from 1.42 to 1.78 × 10⁶ g/mol) and compositions was characterized by gel permeation chromatography–multiangle laser light scattering, ¹H NMR and FTIR spectroscopy, and elemental analysis. The surface activity, morphology, and aggregation properties of PAAD samples were measured by surface tension and dynamic light scattering. A schematic representation of the formation of Cr(OH)₃ and its precipitation using PAAD samples as coagulant aid is discussed in the article. In addition, the Cr(OH)₃–copolymer interaction, as investigated by precipitation experiments, demonstrated that these copolymers have good Cr(OH)₃ binding capacity and potential as coagulant aid for the removal of Cr(III) from polluted water. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41028.     

Self-assembly of amphiphilic liquid crystal block copolymers containing a cholesteryl mesogen: Effects of block ratio and solvent

We report on the self-assembly, in water and in bulk, of amphiphilic liquid crystal block copolymers consisting of a cholesterol-based smectic LC polymer block (PAChol) and poly(ethylene glycol) (PEG) block. Two series of block copolymers, PEG₄₅-b-PAChol and PEG₁₁₄-b-PAChol (45 and 114 are the degree of polymerization of PEG blocks) with different hydrophilic/hydrophobic weight ratios were synthesized and characterized in detail. Depending on the diblock composition, smectic polymer vesicles and/or nanofibers were formed by adding water into a dilute solution of copolymers in dioxane. If THF is used instead of dioxane as solvent, solid spherical aggregates were obtained upon water addition for PEG₄₅-b-PAChol series, while macroscopic precipitation occurred for PEG₁₁₄-b-PAChol series. The mesomorphic and microphase segregation structures of the block copolymers in bulk were studied by X-ray scattering, DSC and POM. The interdigital smectic A (SmA_d) phase with a lamellar period of 4.25 nm was detected in all block copolymers. For PEG₁₁₄-b-PAChol₅ (PEG/PAChol weight ratio = 66/34) and PEG₁₁₄-b-PAChol₁₂ (45/55), lamellar type of microphase segregation was observed.     

Micellization and sol-gel transition of novel thermo- and pH-responsive ABC triblock copolymer synthesized by RAFT

A well-defined thermo- and pH-responsive ABC-type triblock copolymer monomethoxy poly(ethylene glycol)-b-poly(2-(2-methoxyethoxy) ethyl methacrylate-co-N-hydroxymethyl acrylamide)-b-poly(2-(diethylamino) ethyl methacrylate), mPEG-b-P(MEO₂MA-co-HMAM)-b-PDEAEMA, was synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT). The ABC-type triblock copolymer was endowed thermo- and pH-responsive, corresponding to the thermosensitive properties of P(MEO₂MA-co-HMAM) and pH-responsive properties PDEAEMA segments, respectively. The thermo- and pH-responsive properties of copolymer aqueous solutions were studied by UV transmittance measurements, dynamic light scattering (DLS), transmission electron microscopy (TEM). The results showed that the N-hydroxymethyl acrylamide (HMAM) content in triblock copolymer affected the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution. The copolymer self-assembled into core-shell micelles, with the thermoresponsive P(MEO₂MA-co-HMAM) block and the hydrophilic PEG block as the shell, the hydrophobic PDEAEMA block as the core, in alkaline solution at room temperature. While in acidic media, when the temperature above the lower critical solution temperature (LCST) of the triblock copolymer aqueous solution, the copolymer self-assembled into P(MEO₂MA-co-HMAM)-core micelles with mixed hydrophilic PEG and pH-responsive PDEAEMA coronas. Sol-gel transition temperature (T_sol-gel) for the triblock copolymer determined by vial inversion test further indicated that it is dependent on the concentration of the triblock copolymers and solution pH. Copolymer hydrogel loaded with bovine serum albumin (BSA) were used for the sustained release study. The results indicated that the hydrogel was a promising candidate for controlling protein drug delivery.     

Self‐assembled structures in blends of disordered and lamellar block copolymers: SAXS,SANS and TEM study

BACKGROUND: The phase behaviour of copolymers and their blends is of great interest due to the phase transitions, self‐assembly and formation of ordered structures. Phenomena associated with the microdomain morphology of parent copolymers and phase behaviour in blends of deuterated block copolymers of polystyrene (PS) and poly(methyl methacrylate) (PMMA), i.e. (dPS‐block‐dPMMA)₁/(dPS‐block‐PMMA)₂, were investigated using small‐angle X‐ray scattering, small‐angle neutron scattering and transmission electron microscopy as a function of molecular weight, concentration of added copolymers and temperature. RESULTS: Binary blends of the diblock copolymers having different molecular weights and different original micromorphology (one copolymer was in a disordered state and the others were of lamellar phase) were prepared by a solution‐cast process. The blends were found to be completely miscible on the molecular level at all compositions, if their molecular weight ratio was smaller than about 5. The domain spacing D of the blends can be scaled with M_n by D ～ M_n^2/3 as predicted by a previously published postulate (originally suggested and proved for blends of lamellar polystyrene‐block‐polyisoprene copolymers). CONCLUSIONS: The criterion for forming a single‐domain morphology (molecularly mixed blend) taking into account the different solubilization of copolymer blocks has been applied to explain the changes in microdomain morphology during the self‐assembling process in two copolymer blends. Evidently the criterion, suggested originally for blends of lamellar polystyrene‐block‐polyisoprene copolymers, can be employed to a much broader range of block copolymer blends. Copyright © 2008 Society of Chemical Industry     

Biodegradable and photocurable multiblock copolymers with shape‐memory properties from poly(ε‐caprolactone) diol,poly(ethylene glycol), and 5‐cinnamoyloxyisophthalic acid

Biodegradable and photocurable multiblock copolymers of various compositions were synthesized by the high‐temperature solution polycondensation of poly(ε‐caprolactone) (PCL) diols of molecular weight (M_n) = 3000 and poly(ethylene glycol)s (PEG) of M_n = 3000 with a dichloride of 5‐cinnamoyloxyisophthalic acid (ICA) as a chain extender, followed by irradiation by a 400 W high‐pressure mercury lamp (λ > 280 nm) to form a network structure. The gel contents increased with photocuring time, reaching a level of over 90% after 10 min for all copolymers without a photoinitiator. The thermal and mechanical properties of the photocured copolymers were examined by DSC and tensile tests. In cyclic thermomechanical tensile tests, the photocured ICA/PCL/PEG copolymer films showed good shape‐memory properties at 37–60°C, with both shape fixity ratio and shape recovery ratio over 90% at a maximum tensile strain of 100–300%. The water absorption of these copolymers and their rate of degradation in a phosphate buffer solution (pH 7.0) at 37°C increased significantly with increasing PEG content. The novel photocured ICA/PCL/PEG multiblock copolymers are potentially useful in biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of double‐hydrophilic poly(methylacrylic acid)–poly(ethylene glycol)–poly(methylacrylic acid) triblock copolymers and their micelle formation

The aim of the work reported was to synthesize a series of double‐hydrophilic poly(methacrylic acid)‐block‐poly(ethylene glycol)‐block‐poly(methacrylic acid) (PMAA‐b‐PEG‐b‐PMAA) triblock copolymers and to study their self‐assembly behavior. These copolymeric self‐assembly systems are expected to be potential candidates for applications as carriers of hydrophilic drugs. Bromo‐terminated difunctional PEG macroinitiators were used to synthesize well‐defined triblock copolymers of poly(tert‐butyl methacrylate)‐block‐poly(ethylene glycol)‐block‐poly(tert‐butyl methacrylate) via reversible‐deactivation radical polymerization. After the removal of the tert‐butyl group by hydrolysis, double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers were obtained. pH‐sensitive spherical micelles with a core–corona structure were fabricated by self‐assembly of the double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers at lower solution pH. Transmission electron microscopy and laser light scattering studies showed the micelles were of nanometric scale with narrow size distribution. Solution pH and micelle concentration strongly influenced the hydrodynamic radius of the spherical micelles (48–310 nm). A possible reason for the formation of the micelles is proposed. Copyright © 2010 Society of Chemical Industry     

Synthesis of amphiphilic triblock copolymers for the formation of magnesium fluoride (MgF2) nanoparticles

A series of amphiphilic poly(2‐hydroxyethyl methacrylate)‐b‐polydimethylsiloxane‐b‐poly(2‐hydroxyethyl methacrylate) (pHEMA‐b‐PDMS‐b‐pHEMA) (A‐B‐A) triblock copolymers were synthesized from three different carbinol‐terminated polydimethylsiloxanes with varying molecular weight. A carbinol‐terminated polydimethylsiloxane was modified with 2‐bromoisobutyryl bromide to obtain a macroinitiator. The block copolymers were characterized by NMR, GPC, and dynamic light scattering (DLS). Reverse micelles of a copolymer were formed in mixture of benzene/methanol solution which served as nanoreactors for the synthesis of magnesium fluoride (MgF₂) nanoparticles. The MgF₂ was prepared via chemical precipitation using magnesium chloride and potassium fluoride as reactants. The MgF₂‐triblock copolymer composites were synthesized as a function of MgF₂–weight ratio (0.5, 5, and 10 wt%) in copolymer. The MgF₂ colloids were dissolved in three organic solvents: methanol, isopropanol, and tetrahydrofuran. The polymer nanoparticles were characterized by DLS, transmission electron microscopy, thermogravimetric analysis, and X‐ray diffraction (XRD) analysis. The formation of MgF₂ crystals was observed by XRD. Particle size and particle size distribution showed significant changes in different solvents. The thermal stability of MgF₂ colloids increased as the amount of nanoparticle increased in polymeric matrix. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012