Influences of extractant on the hydrophilicity and performances of HDPE/PE‐b‐PEG blend membranes prepared via thermally induced phase separation (TIPS) process

Blending the block copolymer into the membrane matrix is a convenient and efficient way for membrane modification. In this study, HDPE/PE‐b‐PEG membranes were prepared via TIPS process, and the extractant effect was investigated. An interesting finding was that a non‐polar extractant (n‐hexane) was more conducive to the surface enrichment of PEG chains than a polar solvent (ethanol). The reason was deemed to be the combined effect of entropy drive, interfacial energy, and the swelling behavior. Besides, membrane performances related to the surface chemical properties were studied. Results suggested that the prepared blend membranes extracted by n‐hexane showed enhanced hydrophilicity, anti‐fouling property and water flux. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2680–2687, 2013     

Effects of the extractant on the hydrophilicity and performance of high‐density polyethylene/polyethylene‐b‐poly(ethylene glycol) blend membranes prepared via a thermally induced phase separation process

The blending of a block copolymer into the membrane matrix is a convenient and efficient way to modify membranes. In this study, high‐density polyethylene/polyethylene‐b‐poly(ethylene glycol) (PEG) membranes were prepared via a thermally induced phase separation process, and the extractant effect was investigated. An interesting finding was that the nonpolar extractant (n‐hexane) was more conducive to the surface enrichment of the PEG chains than the polar solvent (ethanol). The reason was deemed to be the combined effect of the entropy drive, interfacial energy, and swelling behavior. In addition, the membrane performance related to the surface chemical properties was studied. The results suggest that the prepared blend membranes extracted by n‐hexane showed enhanced the hydrophilicity, antifouling properties, and water flux. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3816–3824, 2013     

Crystallization kinetics of PE‐b‐isotactic PMMA diblock copolymer synthesized using SiMe2(Ind)2ZrMe2 and MAO cocatalyst

Polyethylene‐b‐poly(methyl methacrylate) (PE‐b‐PMMA) diblock copolymer has important interfacial applications. Hence, a PE‐b‐isotactic PMMA diblock copolymer was synthesized using SiMe₂(Ind)₂ZrMe₂ and MAO cocatalyst. The polymerization mechanism and the origin of PMMA isotacticity were duly explained. An appropriate nonisothermal Avrami‐Erofeev crystallization model was developed to compare the crystallization kinetics of the above copolymer with that of a PE homopolymer. For both polymers, the model well matched the entire differential scanning calorimeter crystallinity profile, notably for a single Avrami‐Erofeev index, and predicted cylindrical crystal growth. This model particularly overcomes the limitations of the published nonisothermal crystallization models, and provides interesting insight into PE crystallization. The PMMA block significantly decreased the heats of crystallization and fusion, % crystallinity, and the relative crystallization function; increased the nonisothermal crystallization rate constant; and introduced minimal dilution effect whereas the PE block formed a continuous or percolated phase. This study correlates catalyst structure, copolymer block tacticity, and PE nonisothermal crystallization and melting behavior. © 2012 American Institute of Chemical Engineers AIChE J, 59: 200–214, 2013     

Polyethylene‐b‐poly(ethylene glycol) diblock copolymers: New synthetic strategy and application

Polyethylene‐b‐poly (ethylene glycol) (PE‐b‐PEG) was successfully synthesized by a coupling reaction of hydroxyl‐terminated polyethylene (PE‐OH) and isocyanate‐terminated poly (ethylene glycol) (PEG‐NCO). PE‐OH was prepared by coordination chain transfer polymerization (CCTP) using 2,6‐bis[1‐(2,6‐diisopropylphenyl)imino ethyl] pyridine iron (II) dichloride /dry ethylaluminoxane (DEAO) /diethyl zinc (ZnEt₂) as catalyst and subsequent in situ oxidation with oxygen. The active centers of this catalyst system were counted, indicating that the active centers were more stable using DEAO as cocatalyst than using dry methylaluminoxane (DMAO) as cocatalyst. PEG‐NCO was synthesized through the condensation reaction of monomethylpoly(ethylene glycol) (PEG) with isophoronediisocyanate (IPDI). Subsequently, the thermal characterization, morphological characterization and the application of these diblock copolymers was investigated. The results indicated that the diblock copolymers were effective compatilizers for polyethylene/poly(ethylene glycol) blends. Meanwhile, they were excellent surface modification agents for polyethylene membrane and glass sheet, it can efficiently turn a hydrophobic surface into a hydrophilic surface, or vice versa. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42236.     

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     

Poly(ethylene‐graft‐ethylene oxide) (PE‐PEO) and poly(ethylene‐co‐acrylic acid) (PEAA) as compatibilizers in blends of LDPE and polyamide‐6

In a blend of two immiscible polymers a controlled morphology can be obtained by adding a block or graft copolymer as compatibilizer. In the present work blends of low‐density polyethylene (PE) and polyamide‐6 (PA‐6) were prepared by melt mixing the polymers in a co‐rotating, intermeshing twin‐screw extruder. Poly(ethylene‐graft‐polyethylene oxide) (PE‐PEO), synthesized from poly(ethylene‐co‐acrylic acid) (PEAA) (backbone) and poly(ethylene oxide) monomethyl ether (MPEO) (grafts), was added as compatibilizer. As a comparison, the unmodified backbone polymer, PEAA, was used. The morphology of the blends was studied by scanning electron microscopy (SEM). Melting and crystallization behavior of the blends was investigated by differential scanning calorimetry (DSC) and mechanical properties by tensile testing. The compatibilizing mechanisms were different for the two copolymers, and generated two different blend morphologies. Addition of PE‐PEO gave a material with small, well‐dispersed PA‐spheres having good adhesion to the PE matrix, whereas PEAA generated a morphology characterized by small PA‐spheres agglomerated to larger structures. Both compatibilized PE/PA blends had much improved mechanical properties compared with the uncompatibilized blend, with elongation at break (ε_b) increasing up to 200%. Addition of compatibilizer to the PE/PA blends stabilized the morphology towards coalescence and significantly reduced the size of the dispersed phase domains, from an average diameter of 20 μm in the unmodified PE/PA blend to approximately 1 μm in the compatibilized blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2416–2424, 2000     

Thermal analysis and non‐isothermal kinetics of poly(ethylene glycol) with different molecular weight

This study focuses on comprehensively investigating polyethylene glycol (PEG) with different molecular weight. Thermal properties of the PEGs were investigated by differential scanning calorimetry (DSC), as well as gradual melting and freezing tests with thermocouples. Results show that the degree of PEG crystallization increased with the increasing of the molecular weight of polymers. The temperatures of pure PEG 1000 and PEG 1000‐PEG 600 blends ranged from 20 to 50°C. The apparent activation energy of pure PEG1000 was 300 kJ/mol, whereas that of the PEG blend was 239 kJ/mol. During the crystallization process, Avrami index n ranged from 5 to 3 and half‐crystallization time t_1/2 decreased with the acceleration of the crystallization rate R. This difference was due to the increase in polydispersity of the PEG system and decrease in the degree of crystallization. POLYM. ENG. SCI., 54:2872–2876, 2014. © 2014 Society of Plastics Engineers     

PE/PE‐g‐MAH/Org‐MMT nanocomposites. II. Nonisothermal crystallization kinetics

The nonisothermal crystallization kinetics of high‐density polyethylene (HDPE) and polyethylene (PE)/PE‐grafted maleic anhydride (PE‐g‐MAH)/organic‐montmorillonite (Org‐MMT) nanocomposite were investigated by differential scanning calorimetry (DSC) at various cooling rates. Avrami analysis modified by Jeziorny, Ozawa analysis, and a method developed by Liu well described the nonisothermal crystallization process of these samples. The difference in the exponent n, m, and a between HDPE and the nanocomposite indicated that nucleation mechanism and dimension of spherulite growth of the nanocomposite were different from that of HDPE to some extent. The values of half‐time (t_1/2), K(T), and F(T) showed that the crystallization rate increased with the increase of cooling rates for HDPE and composite, but the crystallization rate of composite was faster than that of HDPE at a given cooling rate. Moreover, the method proposed by Kissinger was used to evaluate the activation energy of the mentioned samples. It was 223.7 kJ/mol for composite, which was much smaller than that for HDPE (304.6 kJ/mol). Overall, the results indicated that the addition of Org‐MMT and PE‐g‐MAH could accelerate the overall nonisothermal crystallization process of PE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3054–3059, 2004     

Synthesis and characterization of PES/PSF/PEG by immersion precipitation for Mediterranean seawater desalination by FO membrane

In the present study, a simple, inexpensive, nontoxic, and environmentally friendly polyethylene glycol (PEG) polymer was used to enhance the hydrophilicity of the forward osmosis (FO) membrane using various PEG concentrations as a pore forming agent in the casting solution of polyethersulfone/polysulfone (PES/PSF) blend membranes. A nonwoven PES/PSF FO blend membrane was fabricated via the immersion precipitation phase inversion technique. The membrane dope solution was cast on polyethylene terephthalate (PET) nonwoven fabric. The results revealed that PEG is a pore forming agent and that adding PEG promotes membrane hydrophilicity. The membrane with 1 wt% PEG (PEG1) had about 27% lower contact angle than the pristine blend membrane. The PEG1 membrane has less tortuosity (which reduces from 3.4–2.73), resulting in a smaller structure parameter (S value) of 277 μm, due to the presence of open pores on the bottom surface structure, which results in diminished ICP. Using 1 M NaCl as the draw solution and distilled water as the feed solution, the PEG1 membrane exhibited higher water flux (136 L m⁻² h⁻¹) and lower reverse salt flux (1.94 g m⁻² h⁻¹). Also, the selectivity of the membrane, specific reverse salt flux, (J_s/J_w) showed lower values (0.014 g/L). Actually, the PEG1 membrane has a 34.6% higher water flux than the commercial nonwoven-cellulose triacetate (NW-CTA) membrane. By means of varied concentrations of NaCl salt solution (0.6, 1, 1.5, and 2 M), the membrane with 1 wt% PEG showed improved FO separation performance with permeate water fluxes of 108, 136, 142, and 163 L m⁻² h⁻¹. In this work, we extend a promising gate for designing fast water flux PES/PSF/PEG FO blend membranes for water desalination.     

Investigation of crystallization of PVCH‐PE‐PVCH triblock copolymer in supercritical carbon dioxide

Crystallization of glassy‐crystalline‐glassy poly(vinylcyclohexane)‐b‐polyethylene‐b‐poly(vinylcyclo hexane) (PVCH‐PE‐PVCH) triblock copolymer treated in supercritical Carbon Dioxide (scCO₂) was investigated by using differential scanning calorimetry (DSC) and atomic force microscope (AFM). It was found that the melting temperatures (T_m) and the crystallinity (X_c) of the PVCH‐PE‐PVCH samples treated in scCO₂ at different annealing temperatures (T) were all much higher than those of the untreated PVCH‐PE‐PVCH, indicating that the scCO₂ could effectively induce the samples to further crystallize. With increasing the T, the T_m of the samples linearly increased, even up to 108°C, close to the T_m (～ 110°C) of the PE homopolymer hydrogenated from polybutadiene which is equal to the PE block in the triblock copolymer. The results could be ascribed to the released PE chain ends linked to the PVCH block due to the lowered T_g of the PVCH block swollen by scCO₂. It suggested that the origin of the confined crystallization in PVCH‐PE‐PVCH was the fixed PE chain ends by the glassy PVCH. AFM images of the samples treated in scCO₂ showed that the PVCH lamella phase tended to connect each other and led to the aggregated structures. The result indicated that the PVCH block could be availably swollen by scCO₂. It supported the DSC experiment results of the samples treated in scCO₂. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 102: 2584–2589, 2006     

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     

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     

Gasoline permeation behavior and mechanical properties of polyamide 6/nanoclay,polyamide 6/PE‐g‐maleic anhydride blend,and polyamide 6/PE‐g‐maleic anhydride/clay nanocomposite

In this article, polyamide 6 (PA6)/clay nanocomposites, PA6/polyethylene grafted maleic anhydride (PE‐g‐MA) blends, and PA6/PE‐g‐MA/clay nanocomposites were prepared and their gasoline permeation behavior and some mechanical properties were investigated. In PA6/clay nanocomposites, cloisite 30B was used as nanoparticles, with weight percentages of 1, 3, and 5. The blends of PA6/PE‐g‐MA were prepared with PE‐g‐MA weight percents of 10, 20, and 30. All samples were prepared via melt mixing technique using a twin screw extruder. The results showed that the lowest gasoline permeation occurred when using 3 wt % of nanoclay in PA6/clay nanocomposites, and 10 wt % of PE‐g‐MA in PA6/PE‐g‐MA blends. Therefore, a sample of PA6/PE‐g‐MA/clay nanocomposite containing 3 wt % of nanoclay and 10 wt % of PE‐g‐MA was prepared and its gasoline permeation behavior was investigated. The results showed that the permeation amount of PA6/PE‐g‐MA/nanoclay was 0.41 g m^?2 day^?1, while this value was 0.46 g m^?2 day^?1 for both of PA6/3wt % clay nanocomposite and PA6/10 wt % PE‐g‐MA blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40150.     

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.     

Morphology and properties of nylon 6 and high density polyethylene blends in presence of nanoclay and PE‐g‐MA

In this study, we report the synergistic effect of nanoclay and maleic anhydride grafted polyethylene (PE‐g‐MA) on the morphology and properties of (80/20 w/w) nylon 6/high density polyethylene (HDPE) blend. Polymer blend nanocomposites containing nanoclay with and without compatibilizer (PE‐g‐MA) were prepared by melt mixing, and their morphologies and structures were examined with scanning electron microscopy (SEM) and wide angle X‐ray diffractometer (WAXD) study. The size of phase‐separated domains decreased considerably with increasing content of nanoclay and PE‐g‐MA. WAXD study and transmission electron microscopy (TEM) revealed the presence of exfoliated clay platelets in nylon 6 matrix, as well as, at the interface of the (80/20 w/w) nylon 6/HDPE blend–clay nanocomposites. Addition of PE‐g‐MA in the blend–clay nanocomposites enhanced the exfoliation of clays in nylon 6 matrix and especially at the interface. Thus, exfoliated clay platelets in nylon 6 matrix effectively restricted the coalescence of dispersed HDPE domains while PE‐g‐MA improved the adhesion between the phases at the interface. The use of compatibilizer and nanoclay in polymer blends may lead to a high performance material which combines the advantages of compatibilized polymer blends and the merits of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of annealing at 135° on the mechanical properties of injection molded high density polyethylene-polypropylene blends

The effect of annealing at 135°C for 5 hours on the tensile properties of mechanically mixed and then injection molded high density polyethylene (HDPE) and polypropylene (PP) blends has been investigated. Both the tangent elastic modulus and the tensile strength at yield exhibit a non-linear behavior versus blend composition with a minimum of properties typical for incompatible blends. Annealing substantially improves mechanical properties of pure components and blends (20 percent increase in the yield strength of pure components and blends and the modulus of pure components, and ～40 percent increase in the modulus of 50/50 blends) but the property behavior versus composition is still nonlinear. Scanning electron microscopy studies of fracture surfaces of blends seems to indicate some improvement in bonding between phases as a result of annealing, Both the elastic modulus and yield strength fit extremely well to the modified “rule of mixtures” equation in the general form: M_b = M_PEφ_PE + M_PPφ_PP + ΔM_PE/PPφ_PEφ_PP where M_b is the blend property, M_PE and M_PP are properties of pure PE and PP components, φ_PE and φ_PP are weight fractions of PE and PP, and ΔM_PE/PP is the interaction term being a measure of the deviation from simple additivity.     

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     

Synthesis and characterization of poly(ϵ‐caprolactone)‐b‐poly(ethylene glycol) block copolymers prepared by a salicylaldimine‐aluminum complex

A series of poly(?‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) block copolymers with different molecular weights were synthesized with a salicylaldimine‐aluminum complex in the presence of monomethoxy poly(ethylene glycol). The block copolymers were characterized by ¹H NMR, GPC, WAXD, and DSC. The ¹H NMR and GPC results verify the block structure and narrow molecular weight distribution of the block copolymers. WAXD and DSC results show that crystallization behavior of the block copolymers varies with the composition. When the PCL block is extremely short, only the PEG block is crystallizable. With further increase in the length of the PCL block, both blocks can crystallize. The PCL crystallizes prior to the PEG block and has a stronger suppression effect on crystallization of the PEG block, while the PEG block only exerts a relatively weak adverse effect on crystallization of the PCL block. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Miscibility of block copolymers of poly(ε‐caprolactone) and poly(ethylene glycol) with poly(3‐hydroxybutyrate) as well as the compatibilizing effect of these copolymers in blends of poly(ε‐caprolactone) and poly(3‐hydroxybutyrate)

Atactic poly(3‐hydroxybutyrate) (a‐PHB) and block copolymers of poly(ethylene glycol) (PEG) with poly(ε‐caprolactone) (PCL‐b‐PEG) were synthesized through anionic polymerization and coordination polymerization, respectively. As demonstrated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) measurements, both chemosynthesized a‐PHB and biosynthesized isotactic PHB (i‐PHB) are miscible with the PEG segment phase of PCL‐b‐PEGs. However, there is no evidence showing miscibility between both PHBs and the PCL segment phase of the copolymer even though PCL has been block‐copolymerized with PEG. Based on these results, PCL‐b‐PEG was added, as a compatibilizer, to both the PCL/a‐PHB blends and the PCL i‐PHB blends. The blend films were obtained through the evaporation of chloroform solutions of mixed components. Excitingly, the improvement in mechanical properties of PCL/PHB blends was achieved as anticipated initially upon the addition of PCL‐b‐PEG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2600–2608, 2001     

Crystallization behavior of PEO in blends of poly(ethylene oxide)/poly(2‐vinyl pyridine)‐b‐(ethylene oxide) block copolymer

The crystallization behavior of two molecular weight poly(ethylene oxide)s (PEO) and their blends with the block copolymer poly(2‐vinyl pyridine)‐b‐poly(ethylene oxide) (P2VP‐b‐PEO) was investigated by polarized optical microscopy, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy (AFM). A sharp decreasing of the spherulite growth rate was observed with the increasing of the copolymer content in the blend. The addition of P2VP‐b‐PEO to PEO increases the degradation temperature becoming the thermal stability of the blend very similar to that of the block copolymer P2VP‐b‐PEO. Glass transition temperatures, T_g, for PEO/P2VP‐b‐PEO blends were intermediate between those of the pure components and the value increased as the content of PEO homopolymer decreased in the blend. AFM images showed spherulites with lamellar crystal morphology for the homopolymer PEO. Lamellar crystal morphology with sheaf‐like lamellar arrangement was observed for 80 wt% PEO(200M) and a lamellar crystal morphology with grain aggregation was observed for 50 and 20 wt% blends. The isothermal crystallization kinetics of PEO was progressively retarded as the copolymer content in the blend increased, since the copolymer hinders the molecular mobility in the miscible amorphous phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers