Synthesis and characterization of a novel amphiphilic poly (ethylene glycol)–poly (ε-caprolactone) graft copolymers

A series of amphiphilic graft copolymers PEO-g-PCL with different poly (ε-caprolactone) (PCL) molecular weight were successfully synthesized by a combination of anionic ring-opening polymerization (AROP) and coordination-insertion ring-opening polymerization. The linear PEO was produced by AROP of ethylene oxide (EO) and ethoxyethyl glycidyl ether initiated by 2-(2-methoxyethoxy) ethoxide potassium, and the hydroxyl groups on the backbone were deprotected after hydrolysis. The ring-opening polymerization of CL was initiated using the linear poly (ethylene oxide) (PEO) with hydroxyl group on repeated monomer as macroinitiator and Sn(Oct)₂ as catalyst, then amphiphilic graft copolymers PEO-g-PCL were obtained. By changing the ratio of monomer and macroinitiator, a series of PEO-g-PCL with well-defined structure, molecular weight control, and narrow molecular weight distribution were prepared. The expected intermediates and final products were confirmed by ¹H NMR and GPC analyzes. In addition, these amphiphilic graft copolymers could form spherical aggregates in aqueous solution by self-assemble, which were characterized by transmission electron microscopy, and the critical micelle concentration values of graft copolymers PEO-g-PCL were also examined in this article.     

Ultrafiltration Membranes Coated by Amphiphilic Copolymers Containing Superhydrophilic Zwitterionic and Hydrophobic POSS Moieties Showing Improved Fouling Resistance/Release Properties

Ultrafiltration membranes coated with amphiphilic copolymers containing superhydrophilic zwitterionic moieties and hydrophobic POSS moieties (PSM‐coated membranes) are prepared. The free radical polymerization of 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and 3‐(3,5,7,9,11,13,15‐heptaisobutylpentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]octasiloxane‐1‐yl)propyl methacrylate (MAPOSS) monomers is used to prepare a series of copolymers containing different compositions of DMAEMA and MAPOSS units (PDMs). The DMAEMA units in the PDM‐coated membranes are subsequently converted to sulfobetaine methacrylate (SBMA) units using 1,3‐propane sultone (post‐zwitterionization) to give the PSM‐coated membranes. The PSM‐coated membranes show improved fouling resistance/release properties, compared with a neat polysulfone (PSf) membrane. The improved fouling resistance properties of the PSM‐coated membranes are attributed to the superhydrophilic zwitterionic moieties, which form a hydration layer on the membrane surface via electrostatic interactions between the zwitterions and water molecules. Moreover, the total surface energy (γ_S) value of the PSM‐coated membrane is smaller than that of the PSf membrane due to the hydrophobic POSS moieties. This results in the superior fouling release properties of the PSM‐coated membranes.     

Synthesis and characterization of a poly(ether–ester) copolymer from poly(2,6 dimethyl‐1,4‐phenylene oxide) and poly(ethylene terephthalate)

A series of poly(ether–ester) copolymers were synthesized from poly(2,6 dimethyl‐1,4‐phenylene oxide) (PPO) and poly(ethylene terephthalate) (PET). The synthesis was carried out by two‐step solution polymerization process. PET oligomers were synthesized via glycolysis and subsequently used in the copolymerization reaction. FTIR spectroscopy analysis shows the coexistence of spectral contributions of PPO and PET on the spectra of their ether–ester copolymers. The composition of the poly(ether–ester)s was calculated via ¹H NMR spectroscopy. A single glass transition temperature was detected for all synthesized poly(ether–ester)s. T_g behavior as a function of poly(ether–ester) composition is well represented by the Gordon‐Taylor equation. The molar masses of the copolymers synthesized were calculated by viscosimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and physicochemical characterization of amphiphilic block copolymer self‐aggregates formed by poly(ethylene glycol)‐block‐poly(ϵ‐caprolactone)

Diblock copolymers with different poly(ε‐caprolactone) (PCL) block lengths were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of monomethoxy poly(ethylene glycol) (mPEG‐OH, MW 2000) as initiator. The self‐aggregation behaviors and microscopic characteristics of the diblock copolymer self‐aggregates, prepared by the diafiltration method, were investigated by using ¹H NMR, dynamic light scattering (DLS), and fluorescence spectroscopy. The PEG–PCL block copolymers formed the self‐aggregate in an aqueous environment by intra‐ and/or intermolecular association between hydrophobic PCL chains. The critical aggregation concentrations of the block copolymer self‐aggregate became lower with increasing hydrophobic PCL block length. On the other hand, reverse trends of mean hydrodynamic diameters were measured by DLS owing to the increasing bulkiness of the hydrophobic chains and hydrophobic interaction between the PCL microdomains. The partition equilibrium constants (K_v) of pyrene, measured by fluorescence spectroscopy, revealed that the inner core hydrophobicity of the nanoparticles increased with increasing PCL chain length. The aggregation number of PCL chain per one hydrophobic microdomain, investigated by the fluorescence quenching method using cetylpyridinium chloride as a quencher, revealed that 4–20 block copolymer chains were needed to form a hydrophobic microdomain, depending on PCL block length. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3520–3527, 2006     

Synthesis of biodegradable and biocompatible ABC triblock copolymers

A facile approach is offered to synthesize well‐defined amphiphilic ABC triblock copolymers composed of poly(ethylene glycol) monomethyl ether (MPEO) as A block, poly(L ‐lysine) (PLLys) as B block, and poly(ε‐caprolactone) (PCL) as C block by a combination of ring‐opening polymerization (ROP) and click reactions. The propargyl‐terminated poly(Z‐L ‐lysine)‐block‐poly(ε‐caprolactone) (MPEO‐PzLLys‐PCL) diblock copolymers were synthesized via the ring‐opening polymerization of N^ε‐carbobenzoxy‐L ‐lysine N‐carboxyanhydride (Z‐L ‐Lys NCA) in DMF at room temperature using propargyl amine as an initiator and the resulting amino‐terminated poly(Z‐L ‐lysine) then used in situ as a macroinitiator for the polymerization of ε‐caprolactone in the presence of stannous octoate as a catalyst. The triblock copolymers poly(ethylene glycol) monomethyl ether –block‐poly(Z‐L ‐lysine)‐block‐poly(ε‐caprolactone) (MPEO‐PzLLys‐PCL) were synthesized via the click reaction of the propargyl‐terminated PzLLys‐PCL and azido‐terminated poly(ethylene glycol) monomethyl ether (PEO‐N₃) in the presence of CuBr and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) catalyst system. After the removal of Z groups of L ‐lysine units, amphiphilic and biocompatible ABC triblock copolymers MPEO‐PLLys‐PCL were obtained. The structural characteristics of these ABC triblock copolymers and corresponding precursors were characterized by NMR, IR, and GPC. These results showed the click reaction was highly effective. Therefore, a facile approach is offered to synthesize amphiphilic and biocompatible ABC triblock copolymers consisting of polyether, polypeptide and polyester. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Functionalized micelles from new ABC polyglycidol-poly(ethylene oxide)-poly(d,l-lactide) terpolymers

New ABC type terpolymers of poly(ethoxyethyl glycidyl ether)/poly(ethylene oxide)/poly(d,l-lactide) were obtained by multi-mode anionic polymerization. After successive deprotection of the ethoxyethyl groups from the first block, highly hydroxyl functionalized copolymers of polyglycidol/poly(ethylene oxide)/poly(d,l-lactide) were obtained. These copolymers form elongated ellipsoidal micelles by direct dissolution in water. The micelles consist of a poly(d,l-lactide) core and stabilizing shell of polyglycidol/poly(ethylene oxide). The hydroxyl groups of polyglycidol blocks situated at the micelle surface provide high functionality, which could be engaged in further chemical modification resulting in a potential drug targeting agents. The micellization process of the copolymers in aqueous media was studied by hydrophobic dye solubilization, static and dynamic light scattering, and transmission electron microscopy.     

Association behavior of thermo-responsive block copolymers based on poly(vinyl ethers)

Thermo-sensitive nanosized structures have been prepared in water from poly(methyl vinyl ether)-block-poly(isobutyl vinyl ether) (PMVE-b-PIBVE) block copolymers. The composition and the architecture (diblock and triblock architectures) of the PMVE-b-PIBVE copolymers have been varied. The investigated copolymers had an asymmetric composition with a major PMVE block. While the PIBVE blocks are hydrophobic, the PMVE blocks are hydrophilic at room temperature and become hydrophobic above their demixing temperature (around 36 °C) as a result of the lower critical solution temperature (LCST) behavior. At room temperature, the amphiphilic copolymers aggregate in water above a critical micelle concentration, which has been experimentally measured by hydrophobic dye solubilization. The hydrodynamic diameter of the structures formed above the cmc has been measured by dynamic light scattering (DLS) while their morphology has been studied by transmission electron microscopy (TEM). ¹H NMR measurements in D₂O at room temperature reveal that the aggregates contain PIBVE insoluble regions surrounded by solvated PMVE chains. These investigations have shown that polydisperse spherical micelles are formed for asymmetric PMVE-b-PIBVE copolymers containing at least 9 IBVE units. For copolymers containing less IBVE units, loose aggregates are formed.Finally, the thermo-responsive, reversible properties of these structures have been investigated. Above the cloud point of the copolymers, the loose aggregates precipitate while the micelles form large spherical structures.     

Poly(allyl glycidyl ether)‐block‐poly(ethylene oxide): A novel promising polymeric intermediate for the preparation of micellar drug delivery systems

Novel diblock copolymers designed for the preparation of micellar drug delivery systems, consisting of hydrophobic poly(allyl glycidyl ether) (PAGE) and hydrophilic poly(ethylene oxide) (PEO), were prepared, and their self‐assembly into micellar structures was studied. Copolymers differing in the length of the polymer blocks were purified and characterized. These amphiphilic copolymers with narrow molecular weight distributions were prepared through the anionic polymerization of allyl glycidyl ether with PEO monomethyl ether sodium salt as the macroinitiator. The PAGE–PEO copolymer readily formed small micelles with narrow size distributions via simple dissolution in water. The addition of pendant double bonds to the hydrophobic part of the chain was intended for further covalent modifications. Catalytic hydrogenation, the radical crosslinking of the micelle core, and the addition of thiol to double bonds of the copolymer were examples of such modifications that were proved to proceed with a quantitative yield for this copolymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 201–211, 2005     

Surface behavior and micelle morphology of novel nonionic polyurethane bolaform amphiphilic block copolymers

A novel series of nonionic bolaamphiphiles—polyurethane amphiphilic block copolymers were synthesized by addition polymerization. Their chemical structures were characterized using FTIR and ¹H-NMR spectra. The critical micelle concentration was determined by surface tensiometer and UV-vis absorption spectra. The surface behaviors of copolymers at air/water interface were also investigated including the effects of concentration, molecular structure, electrolytes, and rest time. The results show that these bolaform polyurethane amphiphilic block copolymers exhibited excellent surface activity: PU₃₄ could attain surface tension as low as 35.6 mN m⁻¹. According to the images of Transmission Electron Microscopy (TEM), the copolymers could self-assemble star-like aggregates comprised of hydrophobic block PPO surrounded by hydrophilic block PEO. Moreover, variation of concentration, the weight fraction of the hydrophilic block (f_phil), and the molecular weight of the copolymers could lead to the transformation of micelle (or premicelle) morphology. This provides a new and simple way to obtain nanoparticles with control over structure on the nanometer scale.     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry     

Synthesis of amphiphilic pseudopolyamino acid‐containing ABC‐triblock copolymers and micellar characterizations

This study describes the synthesis of amphiphilic ABC‐triblock copolymers comprising a central pseudopoly(4‐hydroxy‐L ‐proline) segment and terminal hydrophilic poly(ethylene glycol)methyl ether as well as hydrophobic poly(ε‐caprolactone) blocks. Differential scanning calorimetry, ¹H‐NMR spectroscopy, and gel permeation chromatography are used to characterize the copolymers. The thermal properties (T_g and T_ms) of the triblock copolymers depend on the composition of polymers. Larger amounts of ε‐CL incorporated into the macromolecular backbone increased T_g and T_ms. Fluorescence spectroscopy, transmission electron microscopy, and dynamic light scattering are utilized to investigate their micellar characteristics in the aqueous phase. Observations showed a higher critical micelle concentration with higher hydrophilic components in the copolymers. The micelle exhibited a core‐shell‐corona and/or vesicle shape, and the average size was less than 300 nm. Drug entrapment efficiency and drug loading of micelles depending on the composition of block polymers are also described. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(arylene ether sulfone) multi-block copolymers bearing perfluoroalkylsulfonic acid groups

Poly(arylene ether sulfone) (PAES) multi-block copolymers bearing perfluoroalkylsulfonic acid moieties were prepared from hydrophilic and hydrophobic prepolymers. The latter were synthesized by reaction of N,N-diisopropylethylammonium 2,2-bis(p-hydroxyphenyl)pentafluoropropanesulfonate (HPPS) with bis-(4-fluorophenyl) sulfone (FPS), and biphenol (BP) with FPS, respectively. Prepolymers and multi-block copolymers were prepared at 180 °C in N,N-dimethylacetamide in the presence of K₂CO₃. The prepolymers were reacted overnight; the multi-block copolymers were reacted only 80 min to minimize transetherification. Prepolymers and multi-block copolymers were characterized using ¹H and ¹³C NMR. ¹⁹F NMR provided molecular weight of hydrophilic prepolymers bearing aryl fluoride end groups. GPC was used to characterize the multi-block copolymers. Copolymer block lengths were determined by quantifying ¹³C NMR peak areas of quaternary carbon atoms adjacent to sulfur in FPS moieties. Hydrophilic and hydrophobic block lengths were in the range 9.4-23.4 and 4.4-11.8 repeating units, respectively. AFM showed phase separation for all block lengths. Conductivity at 80 °C and 100% relative humidity ranged from 6.2 to 34.3 mS/cm, with the best value obtained for hydrophilic/hydrophobic block lengths of 13.3/6.0.     

A novel thermosensitive triblock copolymer from 100% renewably sourced poly(trimethylene ether) glycol

Bio‐based amphiphilic triblock copolymers with 100% renewably sourced poly(trimethylene ether) glycol (PO3G) as the hydrophobic blocks and statistical copolymer of 2‐(2‐methoxyethoxy)ethyl methacrylate (MEO₂MA) and oligo(ethylene glycol)methacrylate (OEGMA) [P(MEO₂MA‐stat‐OEGMA)] as the hydrophilic blocks are synthesized and characterized. It is found that the molar ratio of MEO₂MA/OEGMA among the resulting copolymers is approximately 70/30. The degree of polymerization (DP) of P(MEO₂MA‐stat‐OEGMA) block ranges from 16 to 90, and the DP of PO3G block is fixed at 35. The amphiphilic copolymers could form core‐shell micelles self‐assembly in aqueous solution at low concentrations, and the micelles are in spherical shape with sizes varying from 121 to 188 nm. With the increasing length of hydrophilic blocks, the critical micelle concentration increases from 2.15 to 13.8 mg L^?1, and the lower critical solution temperature improves from 32.5 to 38.4 °C. The in vitro doxorubicin (DOX) release study shows that all DOX‐loaded micelles have a higher release rate at 37 °C than that at 25 °C. Cytotoxicity test reveals that the blank micelles are nearly nontoxic. These results indicate that the block copolymer micelles containing 100% renewably sourced PO3G can serve as a potential drug delivery carrier. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46112.     

Self‐assembled micelles prepared from poly(ɛ‐caprolactone)–poly(ethylene glycol) and poly(ɛ‐caprolactone/glycolide)–poly(ethylene glycol) block copolymers for sustained drug delivery

A series of poly(?‐caprolactone)–poly(ethylene glycol) (PCL‐PEG) and poly(?‐caprolactone/glycolide)–poly(ethylene glycol) [P(CL/GA)‐PEG] diblock copolymers were prepared by ring‐opening polymerization of ?‐caprolactone or a mixture of ?‐caprolactone and glycolide using monomethoxy PEG (mPEG) as macroinitiator and Sn(Oct)₂ as catalyst. The resulting copolymers were characterized using ¹H‐NMR, gel permeation chromatography, differential scanning calorimetry, and wide‐angle X‐ray diffraction. Copolymer micelles were prepared using the nanoprecipitation method. The morphology of the micelles was spherical or worm‐like as revealed by transmission electron microscopy, depending on the copolymer composition and the length of the hydrophobic block. Introduction of the glycolide component, even in small amounts (CL/GA = 10), disrupted the chain structure and led to the formation of spherical micelles. Interestingly, the micelle size decreased with the encapsulation of paclitaxel. Micelles prepared from mPEG5000‐derived copolymers exhibited better drug loading properties and slower drug release than those from mPEG2000‐derived copolymers. Drug release was faster for copolymers with shorter PCL blocks than for those with longer PCL chains. The introduction of glycolide moieties enhanced drug release, but the overall release rate did not exceed 10% in 30 days. In contrast, drug release was enhanced in acidic media. Therefore, these bioresorbable micelles and especially P(CL/GA)‐PEG micelles with excellent stability, high drug loading content, and prolonged drug release could be promising for applications as drug carriers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45732.     

Synthesis and characterization of homo‐ and copolymers of 3‐(2‐cyano ethoxy)methyl‐ and 3‐[methoxy(triethylenoxy)]methyl‐3′‐methyl‐oxetane

Two oxetane‐derived monomers 3‐(2‐cyanoethoxy)methyl‐ and 3‐(methoxy(triethylenoxy)) methyl‐3′‐methyloxetane were prepared from the reaction of 3‐methyl‐3′‐hydroxymethyloxetane with acrylonitrile and triethylene glycol monomethyl ether, respectively. Their homo‐ and copolyethers were synthesized with BF₃· Et₂O/1,4‐butanediol and trifluoromethane sulfonic acid as initiator through cationic ring‐opening polymerization. The structure of the polymers was characterized by FTIR and¹H NMR. The ratio of two repeating units incorporated into the copolymers is well consistent with the feed ratio. Regarding glass transition temperature (T_g), the DSC data imply that the resulting copolymers have a lower T_g than pure poly(ethylene oxide). Moreover, the TGA measurements reveal that they possess in general a high heat decomposition temperature. The ion conductivity of a sample (P‐AN 20) is 1.07 × 10^?5 S cm^?1 at room temperature and 2.79 × 10^?4 S cm^?1 at 80 °C, thus presenting the potential to meet the practical requirement of lithium ion batteries for polymer electrolytes. Copyright © 2005 Society of Chemical Industry     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 2. Poly(2‐(dimethylamino)ethyl methacrylate) grafted poly(methyl methacrylate‐co‐2‐hydroxyethyl methacrylate) copolymers and their association behavior in aqueous solution

Narrow‐distribution, well‐defined comb‐like amphiphilic copolymers are reported in this work. The copolymers are composed of poly(methyl methacrylate‐co‐2‐hydroxyethyl methacrylate) (P(MMA‐co‐HEMA)) as the backbones and poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) as the grafted chains, with the copolymer backbones being synthesized via atom‐transfer radical polymerization (ATRP) and the grafted chains by oxyanionic polymerization. The copolymers were characterized by gel permeation chromatography (GPC), Fourier‐transform infrared (FT‐IR) spectroscopy and ¹H NMR spectroscopy. The aggregation behavior in aqueous solutions of the comb‐like amphiphilic copolymers was also investigated. ¹H NMR spectroscopic and surface tension measurements all indicated that the copolymers could form micelles in aqueous solutions and they possessed high surface activity. The results of dynamic light scattering (DLS) and scanning electron microscopy (SEM) investigations showed that the hydrodynamic diameters of the comb‐like amphiphilic copolymer aggregates increased with dilution. Because of the protonizable properties of the graft chains, the surface activity properties and micellar state can be easily modulated by variations in pH. Copyright © 2004 Society of Chemical Industry     

Synthesis and characterization of the feed ratio of polyethylene oxide (0 ∼ 10 wt % PEO) in the nylon‐6/PEO copolymer system

In this work, we have synthesis nylon‐6/polyethylene oxide (PEO) copolymer system based on feed ratio of PEO (0～ 10 wt %) through condensation polymerization in a pilot scale. The structure of copolymer was confirmed by Fourier transform infrared (FTIR) spectroscopy and verified by ¹H nuclear magnetic resonance (¹HNMR). The thermal properties were investigated by differential scanning calorimetry (DSC) and indicated both melting temperature (T_m) and cold crystallization temperature (T_c) appearing unapparent decreased while increased PEO content in copolymers. The incorporation of PEO into the nylon‐6 chain reduced its tensile strength, modulus, and heat distortion temperature (HDT). The notched Izod impact strength of and ductility of the copolymers improved significantly as the PEO content was increased. The plasticizing effect was caused by the soft segments from PEO, which increases the mobility of the molecular chain in the copolymers. The results of mechanical tests agree closely with dynamic mechanical analysis (DMA) measurements. A rheological investigation revealed that neat nylon‐6 and its copolymer displayed similar behavior. The crystalline structure was examined by wide‐angle X‐ray diffraction (WAXD). The results demonstrate that the addition of a little PEO altered the crystallization from the α form to the γ form, mainly owing to the breaking parts of the original H‐bonds by the incorporation of ether groups. A mechanism of interaction between the amide and the ether group in nylon‐6/PEO copolymers is proposed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Amphiphilic star‐shaped poly(ε‐caprolactone)‐block‐poly(l‐lysine) copolymers with porphyrin core: Synthesis,self‐assembly,and cell viability assay

Star‐shaped copolymers poly(ε‐caprolactone)‐bolck‐poly(ε‐benzyloxycarbonyl‐l ‐lysine) (SPPCL‐b‐PZLLs) with porphyrin core were synthesized by a sequential ring‐opening polymerization (ROP) of CL and Nε‐Benzyloxycarbonyl‐l ‐lysine N‐Carboxyanhydride. After the deprotection of benzyloxycarbonyl groups in polylysine blocks, the star‐shaped amphiphilic copolymers SPPCL‐b‐PLLs were obtained. These amphiphilic copolymers can self‐assemble into micelles or aggregates in aqueous solution. Investigation shows that the morphology of micelles/aggregates varied according to the change of pH values of media, indicating the pH‐responsive property of SPPCL‐b‐PLL copolymers. Furthermore, associated with conjugated porphyrin cores, the SPPCL‐b‐PLL copolymers micelles showed a certain degree of Photodynamic Therapy (PDT) effects on tumor cells, suggesting its potential application as carrier for hydrophobic drug with additional therapeutic ability of inherent porphyrin segments. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40097.     

Synthesis and properties of polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene triblock copolymers

A series of well‐defined and property‐controlled polystyrene (PS)‐b‐poly(ethylene oxide) (PEO)‐b‐polystyrene (PS) triblock copolymers were synthesized by atom‐transfer radical polymerization, using 2‐bromo‐propionate‐end‐group PEO 2000 as macroinitiatators. The structure of triblock copolymers was confirmed by ¹H‐NMR and GPC. The relationship between some properties and molecular weight of copolymers was studied. It was found that glass‐transition temperature (T_g) of copolymers gradually rose and crystallinity of copolymers regularly dropped when molecular weight of copolymers increased. The copolymers showed to be amphiphilic. Stable emulsions could form in water layer of copolymer–toluene–water system and the emulsifying abilities of copolymers slightly decreased when molecular weight of copolymers increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 727–730, 2006