Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

Synthesis and coating characteristics of novel calcium‐containing poly(urethane ethers)

Calcium salt of mono(hydroxypentyl)phthalate [Ca(HPP)₂] was synthesized by the reaction of 1,5‐pentanediol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ethers) (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or toluylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HPP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. We synthesized a series of calcium‐containing PUEs with different compositions by taking the molar ratio of Ca(HPP)₂ : PEG₃₀₀ or PEG₄₀₀ : diisocyanate (HMDI or TDI) as 2 : 2 : 4, 3 : 1 : 4, and 1 : 3 : 4 to study the coating properties of the PUEs. Blank PUEs without a calcium‐containing ionic diol were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by fourier transform infrared spectroscopy, ¹HNMR, ^?13C‐NMR, solid‐state cross‐polarity/magic‐angle spinning ¹³C‐NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as a top coat on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, including tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 710–721, 2004     

Synthesis of hydroxyethylcellulose‐graft‐poly(N,N‐dimethylacrylamide) copolymer by ATRP and as dynamic coating in capillary electrophoresis

Hydroxyethylcellulose‐graft‐poly (N, N‐dimethylacrylamide) was synthesized by successive atom transfer radical polymerization (ATRP) of N,N‐dimethylacrylamide (DMA) monomer using HEC‐Br as initiator, CuBr and 5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazamacrocyclotetradecane (Me₆[14]aneN₄) as catalyst and ligand, with molar ratio DMA: HEC‐Br (C? Br): CuBr: Me₆[14]aneN₄ = 100 : 1 : 1 : 3. HEC–Br macroinitiator was synthesized by esterification of HEC with 2‐bromoisobutyryl bromide. GPC and ¹H NMR studies show that the molecular weight of the resulting PDMA increased linearly with the conversion. Within 6 h, the polymerization can reach almost 60% of conversion. The copolymer is applied for the separation of basic proteins in capillary electrophoresis. The results show that this medium has a powerful capability in resisting basic proteins adsorption because the polymer forms noncovalent coating in silica capillaries. With a broad range of pH 2–7, proteins were separated with sufficient efficiencies above 200,000 plates/m. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(dopamine)-assisted preparation of star poly(ethylene glycol)-based coatings: A detailed study of their protein resistance and application in CE

In this study, a set of well-defined multiarm star copolymers, hyperbranched poly(ethylenimine)-graft-poly(ethylene glycol) (bPEI-g-PEG) with different PEG grafting ratios were synthesized. The star PEG-based coatings were then prepared by immobilizing the corresponding copolymers onto poly(dopamine) (PDA)-coated substrates. The chemical composition, hydrophilicity, surface topography, and thickness of the coatings were studied by X-ray photoelectron spectroscopy (XPS), water contact angle (WCA), atomic force microscopy (AFM), and variable angle spectroscopic ellipsometry (VASE), respectively. Furthermore, the surface PEG chain density of star PEG-based coating was evaluated quantitatively and compared with that of linear PEG-based coating. Our results showed that the amount of proteins (albumin from bovine serum, fibrinogen, and lysozyme) adsorbed on the star PEG-based coating as measured by surface plasmon resonance (SPR) was found to be dependent on the surface PEG chain density, which was controlled by the polymer incubation concentrations and PEG grafting ratios. Generally, the star-shaped PEG gave the surface with higher PEG chain density than linear ones and the amount of adsorbed proteins decreased with increasing surface PEG chain density. At last, the star PEG-based coating was successfully applied into the capillary inner surface for protein separation by capillary electrophoresis (CE).     

Characterization and comparison of diblock and triblock amphiphilic copolymers of poly(δ‐valerolactone)

Three types of pegylated amphiphilic copolymers of poly(δ‐valerolactone) (PVL) were copolymerized with methoxy poly(ethylene glycol) (MePEG) and poly(ethylene glycol) (PEG₄₀₀₀ and PEG_10,000), respectively. Pegylation of PVL allowed copolymers possessing amphiphilic property and efficiently self‐assembled to form micelles with a low critical micelle concentration (CMC) in the range of 10^?7–10^?8M. The average molecular weight of copolymers was in the range of 10,000–20,000 Da, and the polydispersity of copolymers was about 1.7–1.8. Higher mobility of low molecular weight PEG (i.e., MePEG and PEG₄₀₀₀) than high molecular weight PEG_10,000 allowed valerolactone ring opening more efficient in terms of PVL/MePEG and PVL/PEG₄₀₀₀ copolymers possessing longer chain length in hydrophobic domain. Pegylated PVL with low CMC and triblock structure was preferred to encapsulate drug during micelle formation. Although all of these amphiphilic copolymers exhibited controlled release character, the micelles formed by triblock copolymer possessed a more stable core‐shell conformation than that by diblock copolymer, and resulted in the release of drug from triblock micelles slower than that from diblock micelles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1836–1841, 2006     

Nonisothermal crystallization behaviors of biodegradable double crystalline poly(butylene succinate)‐poly(ethylene glycol) multiblock copolymers

Nonisothermal crystallization behaviors of both poly(butylene succinate) (PBS) and poly(ethylene glycol) (PEG) segments within PBS‐PEG (PBSEG) multiblock copolymers were investigated by differential scanning calorimetry (DSC). The nonisothermal crystallization kinetics of both PBS and PEG segments were analyzed by Avrami, Ozawa, and Mo methods. The results showed that both of Avrami and Mo methods were successful to describe the nonisothermal crystallization kinetics of PBS and PEG segments. The results of crystallization kinetics indicated that the crystallization rate of PBS segment decreased with PBS segment content and/or L_PBS, while that of PEG segment decreased with M_n,PEG or F_PEG. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40940.     

Lithium ionic conductivity in poly(ether urethanes) derived from poly(ethylene glycol) and lysine ethyl ester

Poly(ether urethanes) obtained by the copolymerization of poly(ethylene glycol) (PEG) and lysine ethyl ester (LysOEt) are elastomeric materials that can be processed readily to form flexible, soft films. In view of these desirable physicomechanical properties, the potential use of these new materials as solid polymer electrolytes was explored. Solid polymer electrolytes were prepared with copolymers containing PEG blocks of different lengths and with different concentrations of lithium triflate (LiCF₃SO₃). Correlations between the length of the PEG block, the concentration of lithium triflate in the formulation, and the observed Li⁺ ion conductivity were investigated. Solid electrolyte formulations were characterized by differential scanning calorimetry for glass transition temperatures (T_g), melting points (T_m), and crystallinity. Ionic conductivity measurements were carried out on thin films of the polymer electrolytes that had been cast on a microelectrode assembly using conventional ac-impedance spectroscopy. These polymer electrolytes showed inherently high ionic conductivity at room temperature. The optimum concentration of lithium triflate was about 25–30% (w/w), resulting at room temperature in an ionic conductivity of about 10⁻⁵ S cm⁻¹. For poly(PEG₂₀₀₀-LysOEt) containing 30% of LiCF₃SO₃, the activation energy was ∼ 1.1 eV. Our results indicate that block copolymers of PEG and lysine ethyl ester are promising candidates for the development of polymeric, solvent-free electrolytes. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1449–1456, 1997     

Synthesis and characterization of amine‐functionalized amphiphilic block copolymers based on poly(ethylene glycol) and poly(caprolactone)

A series of amine‐functionalized block copolymers, poly(caprolactone)‐block‐poly(ethylene glycol) (PCL‐b‐PEG), were synthesized by ring‐opening bulk polymerization (ROP) of ε‐caprolactone (ε‐CL) initiated through the hydroxyl end of the amino poly(ethylene glycol) (PEG) used as a macroinitiator in the presence of stannous 2‐ethylhexonoate [Sn(Oct)₂]. The polymerization and end functionality of the polymer were studied by different physicochemical techniques (¹H NMR, Fourier transform infrared and X‐ray photoelectron spectroscopy, gel permeation chromatography and thermogravimetric analysis). Thermal, crystalline and mechanical properties of the polymer were thoroughly analyzed using differential scanning calorimetry, wide‐angle X‐ray diffractometry and tensile testing, respectively. The results showed a linear improvement in crystallinity and mechanical properties of the polymer with the content of PEG. Thus the synthesized functional polymers can be used as excellent biomaterials for the delivery of polyanions, as well as macroinitiators for the synthesis of A–B–C‐type block copolymers. Copyright © 2006 Society of Chemical Industry     

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     

Competitive hydrogen bonding mechanisms underlying phase behavior of triple poly(N‐vinyl pyrrolidone)–poly(ethylene glycol)–poly(methacrylic acid‐co‐ethylacrylate) blends

Differential scanning calorimetry (DSC) of triple blends of high molecular weight poly(N‐vinyl pyrrolidone) (PVP) with oligomeric poly(ethylene glycol) (PEG) of molecular weight 400 g/mol and copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA) demonstrates partial miscibility of polymer components, which is due to formation of interpolymer hydrogen bonds (reversible crosslinking). Because both PVP and PMAA‐co‐EA are amorphous polymers and PEG exhibits crystalline phase, the DSC examination is informative on the phase state of PEG in the triple blends and reveals a strong competition between PEG and PMAA‐co‐EA for interaction with PVP. The hydrogen bonding in the triple PVP–PEG–PMAA‐co‐EA blends has been established with FTIR Spectroscopy. To evaluate the relative strengths of hydrogen bonded complexes in PVP–PEG–PMAA‐co‐EA blends, quantum‐chemical calculations were performed. According to this analysis, the energy of H‐bonding has been found to diminish in the order: PVP–PMAA‐co‐EA–PEG(OH) > PVP–(OH)PEG(OH)–PVP > PVP–H₂O > PVP–PEG(OH) > PMAA‐co‐EA–PEG(? O? ) > PVP–PMAA‐co‐EA > PMAA‐co‐EA–PEG(OH). Thus, most stable complexes are the triple PVP–PMAA‐co‐EA–PEG(OH) complex and the complex wherein comparatively short PEG chains form simultaneously two hydrogen bonds to PVP carbonyl groups through both terminal OH‐groups, acting as H‐bonding crosslinks between longer PVP backbones. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of hyperbranched poly(3‐methyl‐3‐hydroxymethyloxetane) and their application to separate basic proteins by adsorption coated column

A series of hyperbranched poly(3‐methyl‐3‐hydroxymethyloxetane)s with different degree of branching were synthesized using BF₃·OEt₂ as initiator and coated on the inner surface of the fused‐silica capillaries. In the pH range of 3–9, the coated capillaries reduced electro‐osmotic flow by about four times lower than the bare fused‐silica capillary. The coated capillaries also displayed good resistance to adsorption of cationic proteins, providing clean separations of a mixture of Lysozyme, Cytochrome c, and Ribonuclease A around pH 3–6 in phosphate buffer. The separation efficiency in terms of peak shape was excellent compared with bare fuse‐silica capillary. The separation efficiency of hyperbranched poly(3‐methyl‐3‐hydroxymethyloxetane) with degree of branching of 0.43‐coated capillary column for Lysozyme reached 10⁶ plates/m with a resolution of 7.1, and the coated capillary column had good migration time reproducibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Compatibility,steady and dynamic rheological behaviors of polylactide/poly(ethylene glycol) blends

Understanding the rheological behavior of plasticized polylactide (PLA) contributed to the optimization of processing conditions and revealed the microstructure–property relationships. In this study, the morphological, thermal, steady and dynamic rheological properties of the PLA/poly(ethylene glycol) (PEG) blends were investigated by scanning electron microscope, differential scanning calorimeter, and capillary and dynamic rheometers, respectively. The results illuminated that the melt shear flow basically fitted the power law, whereas the temperature dependence of the apparent shear viscosity (η_a) or complex viscosity (η*) followed the Arrhenius equation. Both the neat PLA and PLA/PEG blends exhibited shear‐thinning behavior. Because the incorporation of PEG reduced the intermolecular forces and improved the mobility of the PLA chains, the η_a, η*, and storage and loss moduli of the PLA/PEG blends decreased. The PEG content (W_PEG) ranged from 0 to 10 wt %, both η_a and η* decreased significantly. However, the decrements of η_a and η* became unremarkable when W_PEG exceeded 10 wt %. The reason was attributed to the occurrence of phase separation, which resulted in the decrease in the plasticization and lubrication efficiencies. This study demonstrated that the addition of the right amount of PEG obviously improved the flow properties of PLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42919.     

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     

Preparation and degradability of poly(lactic acid)–poly(ethylene glycol)–poly(lactic acid)/SiO2 hybrid material

Poly(lactic acid)–poly(ethylene glycol)–poly(lactic acid) (PLA‐PEG‐PLA)/SiO₂ hybrid material is prepared by sol–gel method using tetraethoxysilane (TEOS) and PLA‐PEG‐PLA as raw material. From Fourier transform infrared spectroscopy (FTIR) and X‐ray photoelectron spectroscopy (XPS) spectra, the hydroxyl groups of the silica sol derived from partially hydrolysis of TEOS and the unhydrolyzed ethoxy groups of TEOS can react with PLA‐PEG‐PLA. Differential scanning calorimetry (DSC) curves imply that the glass transition temperature (T_g) of PLA‐PEG‐PLA/SiO₂ hybrid material is higher than that of PLA‐PEG‐PLA and increases with the increase of silica content. X‐ray diffraction (XRD) analysis results show that PLA‐PEG‐PLA and PLA‐PEG‐PLA/SiO₂ hybrid material are both amorphous. Field scanning electron microscope (FSEM) photographs show that when PLA‐PEG‐PLA/SiO₂ hybrid material has been degraded for 12 weeks in normal saline at 37°C, a three‐dimensional porous scaffold is obtained, which is available for cell growth and metabolism. Moreover, the hydroxyl (? OH) groups on SiO₂ of PLA‐PEG‐PLA/SiO₂ hybrid material could buffer the acidity resulted from the degradation of PLA, which is beneficial to proliferation of cell in tissue repairing. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Double‐hydrophilic polyether antiscalant used as a crystal growth modifier of calcium scales in cooling‐water systems

In this study, we synthesized a novel double‐hydrophilic poly(ethylene glycol) (PEG)‐based crystal growth modifier polyethylene glycol double‐ester of maleic anhydride/ acrylic acid named PEGDMA/AA, whose structure was still linear but also had some differences from a traditional chelating linear polymer, in which the PEG segment was incorporated. The scale inhibition behavior of PEGDMA/AA was evaluated by means of a static scale inhibition method. As the polymerization degree of PEG_nDMA was 8 (n = 8), the maximum inhibitory toward calcium carbonate (CaCO₃) and calcium sulfate (CaSO₄) were 89.0 and 98.8% at dosage levels of 12 and 3 mg/L, respectively. Comparisons with other inhibitors were also carried out. Characterization of the CaCO₃ and CaSO₄ scales with scanning electron microscopy and transmission electron microscopy proved that great changes in the size and morphology of the calcium scales took place under the influence of PEG₈DMA/AA. X‐ray diffraction and diffraction patterns further confirmed the impact of PEG₈DMA/AA as a crystal growth modifier. The three supposed mechanisms, (1) chelating solubilization, (2) multilayer type of adsorption, and (3) electrostatic repulsion function, are also described in detail. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39792.     

Synthesis and characterization of biodegradable block copolymers of poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol)

The synthesis of two low molecular weight linear unsaturated oligoester precursors, poly(propylene fumarate‐co‐sebacate) (PPFS) and poly(ethylene fumarate‐co‐sebacate) (PEFS), are described. PPFS, PEFS, and poly(ethylene glycol) are then used to prepare poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PPFS‐co‐PEG) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PEFS‐co‐PEG) block copolymers. The products thus obtained are investigated in terms of the molecular weight, composition, structure, thermal properties, and solubility behavior. A number of design parameters including the molecular weights of PPFS, PEFS, and PEG, the reaction time in the polymer synthesis, and the weight ratio of PEG to PPFS or to PEFS are varied to assess their effects on the product yield and properties. The hydrolytic degradation of PPFS‐co‐PEG and PEFS‐co‐PEG in an isotonic buffer (pH 7.4, 37°C) is investigated, and it is found that the fumarate ester bond cleaves faster than does the sebacate ester bond. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 295–300, 2004     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003     

Crystallization behavior and morphology of poly(lactic acid) with a novel nucleating agent

To improve the crystallization ability of poly(lactic acid) (PLA), a novel nucleating agent with a benzoyl hydrazine compound was used in this study. The crystallization behaviors of PLA/talc and PLA/bibenzoylhydrazinepropane (BBP) with or without poly(ethylene glycol) (PEG) were investigated with differential scanning calorimetry (DSC) and polarized optical microscopy. The DSC curves showed that the crystallization temperature and crystallinity of PLA/BBP (PBBP) was higher than that of PLA/talc. With the addition of PEG, a synergistic effect was found. According to the results of nonisothermal crystallization kinetics, the values of F(T) of PBBP_0.5PEG₅ were usually smaller than those of PTa₃PEG₅, so the nucleation efficiency of BBP was much better than that of talc. From a polarized optical microscopy photo, it was easy to determine that the nucleation density of BBP was higher than that of PTa₃PEG₅, and the spherulitic diameter increased linearly with the crystallization time no matter the impingements. The spherulitic growth rate of PBBP_0.5PEG₅ was faster than that of PTa₃PEG₅, and the induction time of PBBP_0.5PEG₅ was the shortest among all of the samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41367.     

Investigation of poly(lactide) stereocomplexation between linear poly(L‐lactide) and PDLA‐PEG‐PDLA tri‐block copolymer

In this study, stereocomplexed poly(lactide) (PLA) was investigated by blending linear poly(l ‐lactide) (PLLA) and tri‐block copolymer poly(d ‐lactide) ? (polyethylene glycol) ? poly(d ‐lactide) (PDLA‐PEG‐PDLA). Synthesized PDLA‐PEG‐PDLA tri‐block copolymers with different PEG and PDLA segment lengths were studied and their influences on the degree of sterecomplexation and non‐isothermal crystallization behaviour of the PLLA/PDLA‐PEG‐PDLA blend were examined in detail by DSC, XRD and polarized optical microscopy. A full stereocomplexation between PLLA and PDLA‐PEG_4k‐PDLA200 could be formed when the L/D ratio ranged from 7/3 to 5/5 without the presence of PLA homocrystals. The segmental mobility and length of both PEG and PDLA are the dominating factors in the critical D/L ratio to achieve full stereocomplexation and also for nucleation and spherulite growth during the non‐isothermal crystallization process. For fixed PEG segmental length, the stereocomplexed PLA formed showed first an increasing and then a decreasing melting temperature with increasing PDLA segments due to their intrinsic stiff mobility. Furthermore, the effect of PEG segmental mobility on PLA stereocomplexation was investigated. The results clearly showed that the crystallization temperature and melting temperature of stereocomplexed‐PLA kept increasing with increasing PEG segmental length, which was due to PEG soft mobility in the tri‐block copolymers. However, PEG was not favourable for nucleation but could facilitate the spherulite growth rate. Both the PDLA and PEG segmental lengths in the tri‐block copolymers affect the crystallinity of stereocomplexed‐PLA and the stereocomplexation formation process; they have a different influence on blends prepared by solution casting or the melting method. © 2015 Society of Chemical Industry