Hydrolytic degradation of polyester–polyether block copolymer based on polycaprolactone/poly(ethylene glycol)/polylactide

Polyester–polyether block copolymers based on polycaprolactone/poly(ethylene glycol)/polylactide (PCEL) with various compositions were synthesized by direct copolymerization of ϵ‐caprolactone, L ‐lactide and PEG (6000) in the presence of stannous octoate at 130 °C for 56 hr. The degradation behavior of the copolymers was investigated in a pH 7.4 phosphate buffer solution at 37 ±1 °C. Various techniques such as weight, gel permeation chromatography, ¹H nuclear magnetic resonance, differential scanning calorimetry and X‐ray diffractometry were used to monitor the changes in water absorption, weight loss, molar mass, molar mass distribution, thermal properties and compositions. The results show that the hydrophilicity of copolymer was enhanced with increasing poly(ethylene oxide) content, which led to the PEG sequences fast release and an increase in weight loss of the copolymer. Bimodal chromatograms were detected in the degradation, which were attributed to the degradation mechanism of the partial crystalline polymer proceeding predominantly in amorphous zones. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and properties of biodegradable copolymers based on 4,4′‐(adipoyldioxy)dicinnamic acid, 1,6‐hexanediol,and poly(ethylene glycol)s

4,4′‐(Adipoyldioxy)dicinnamic acid (CAC) was synthesized by a condensation of adipoyl chloride and 4‐hydroxycinnamic acid. The CAC6 copolymers were prepared by a high‐temperature solution polycondensation of a diacyl chloride of CAC, 1,6‐hexanediol (6), and poly(ethylene glycol) (PEG) in which the molecular weights of PEG are 1000, 2000, and 8300. Differential scanning calorimetric curves of the copolymers exhibited a glass‐transition temperature because of PEG moiety and two melting endotherms (T_m's); the one at the higher T_m was due to CAC6 moiety, and the other at the lower T_m was due to PEG moiety, suggesting that these copolymers are the block type. The incorporation of the PEG component decreased the tensile strength and initial modulus, but increased the elongation extremely. The enzymatic degradation was performed in phosphate buffer solution (pH 7.2) with Ps. cepacia lipase at 37 °C. The degradation rate of the copolymers increased significantly with an increasing content of PEG, which was correlated to the water absorption of the copolymers. All copolymers could undergo photocuring by ultraviolet (UV) light irradiation (λ > 280 nm) at ambient temperature, as examined by UV spectroscopy and solubility. The CAC6/E2000(50/50) film photocured for 3 min exhibited a good elastic property with a maximum tensile strength of 3.7 MPa and maximum elongation of 640%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2930–2938, 2003     

Synthesis and Enzymatic Degradation of Aliphatic Polyesters Copolymerized with Trimesic Acid

Abstract

Network copolyesters were made from adipic acid and ethylene glycol with 10–40 mol% trimesic acid (Y). Prepolymers prepared by melt polycondensation were cast from dimethylformamide solution and postpolymerized at 260°C for various times to form a network. The degree of reaction (D _R), estimated from the infrared absorbance of hydroxyl and methylene groups, increased with increasing postpolymerization time and leveled out at about 90% after 4–6 hours. Heat distortion temperatures (T _h) measured by thermomechanical analysis increased greatly from ?83 to 48°C upon the incorporation of Y. Wide-angle x-ray diffraction patterns showed that the copolymer films are amorphous. Density, tensile strength, and Young's modulus decreased for the copolymers with 10–30 mol% Y, whereas they increased drastically for the copolymer with 40 mol% Y. The enzymatic degradation was estimated by the weight loss of the copolymer films in buffer solutions with a lipase at 37°C. The weight loss decreased remarkably with increasing Y and showed no weight loss for the copolymer with 40 mol% Y. On the other hand, the weight loss by alkali hydrolysis increased for the copolymers with 10 and 20 mol% Y, implying a difference in the degradation mechanism between enzymatic degradation and alkali hydrolysis.     

Synthesis and properties of monocleavable amphiphilic comblike copolymers with alternating PEG and PCL grafts

Symmetric reduction‐responsive amphiphilic comblike copolymers mid‐disulfide‐functionalized comblike copolymers with alternating copolymer comprised of styrenic unit and N‐(2‐hydroxyethyl) maleimide (HEMI) unit (poly(St‐alt‐HEMI)) backbones and alternating PEG and PCL side chains (S‐CP(PEG‐alt‐PCL)) with poly(St‐alt‐HEMI) backbones and alternating poly(ε‐caprolactone) (PCL) and poly(ethylene glycol) (PEG) side chains were synthesized and used as nanocarriers for in vitro release of doxorubicin. The target copolymers with predetermined molecular weight and narrow molecular weight distribution (M_w/M_n = 1.15–1.20) were synthesized by reversible addition‐fragmentation chain transfer (RAFT) copolymerization of vinylbenzyl‐terminated PEG and N‐(2‐hydroxyethyl) maleimide mediated by a disulfide‐functionalized RAFT agent S‐CPDB, and followed by ring‐opening polymerization of ε‐caprolactone. When compared with linear block copolymer comprised of poly(ethylene glycol) (PEG) and poly(?‐caprolactone) (PCL) segments (PEG‐b‐PCL) copolymers, comblike copolymers with similar PCL contents usually exhibited decreased crystallization temperature, melting temperature, and degree of crystallinity, indicating the significant influence of copolymer architecture on physicochemical properties. Dynamic light scattering measurements revealed that comblike copolymers were liable to self‐assemble into aggregates involving vesicles and micelles with average diameter in the range of 56–226 nm and particle size distribution ranging between 0.07 and 0.20. In contrast to linear copolymer aggregates, comblike copolymer aggregates with similar compositions were of improved storage stability and enhanced drug‐loading efficiency. In vitro drug release confirmed the disulfide‐linked comblike copolymer aggregates could rapidly release the encapsulated drug when triggered by 10 mM DL ‐dithiothreitol. These reduction‐sensitive, biocompatible, and biodegradable aggregates have a potential as controlled delivery vehicles. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of hydrophilic thermotropic block copolyetheresters

The block copolyetheresters with a hard segment of poly (hexamethylene p,p′-bibenzoate) and a soft segment of poly (ethylene oxide) were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, 1,6-hexanediol, and polyethylene glycol (PEG) with molecular weights of 400, 1000, 2000, or 4000. These block copolyetheresters were characterized by intrinsic viscosity, GPC, FT-IR, ¹H-NMR, and water absorption. The thermotropic liquid crystalline properties were investigated by DSC, polarized microscope, and x-ray diffraction. The block copolyetheresters exhibit smectic liquid crystallinity due to the polyester segment. The transitions are dependent on the molar content and the molecular weight of PEG used. The block copolyetheresters show high water absorption due to the hydrophilic nature of the poly (ethylene oxide) segment. The water absorption increases with increasing PEG content. As the molecular weight of PEG increases, the water absorption increases significantly. The results indicate that the water absorption of the poly (ethylene oxide) segment in the block copolymers is affected by the presence of polyester segments. © 1995 John Wiley & Sons, Inc.     

Poly(N-isopropylacrylamide-co-N-t-butylacrylamide)-block-poly(ethylene glycol)-block-poly(N-isopropylacrylamide-co-N-t-butylacrylamide) triblock copolymers: synthesis and thermogelation properties of aqueous solutions

Novel triblock copolymers with PEG middle blocks of 1–10 kDa and poly(N-isopropylacrylamide-co-t-butylacrylamide) statistical copolymer side arms with DP_n?≈?88 and different compositions, were synthesized by SET-LRP. The thermogelation properties of their aqueous solutions depended on both hydrophobic monomer content of the side blocks and molecular weight (MW) of the poly(ethylene glycol) (PEG) middle block, as proven by dynamic rheometry, DSC, and tube inversion method measurements. At constant PEG chain length, increasing TBAM proportions led to a gelation process occurring at progressively lower temperatures, as well as to a lower stability of the forming hydrogels in the case of shorter-PEG-chain block copolymers. By employing longer PEG blocks (M_PEG ≥6,000 Da), stable hydrogels with the gelation temperature below 37 °C could be obtained. For a constant composition of the copolyacrylamide blocks, the dependence of the phase transition temperature (T_ph) on M_PEG displayed a different shape at different polymer solution concentrations, because of the stronger variation of T_ph with polymer concentration as M_PEG increased. Also, the viscoelastic properties of the hydrogels resulting from 20 wt.% polymer aqueous solutions at 37 °C were stronger affected by the MW of the PEG middle block than by the hydrophobic character of the thermosensitive side blocks.     

Synthesis of poly(p-dioxanone)-based block copolymers in supercritical carbon dioxide

Poly(p-dioxanone)–poly(ethylene glycol)–poly(p-dioxanone) triblock copolymers (PPDO–PEG–PPDO) were first synthesized by suspension ring-opening polymerization (ROP) of p-dioxanone (PDO) in supercritical carbon dioxide (scCO₂) using different molecular weights (2–10 K) of poly(ethylene glycol) (PEG) as macroinitiators. White and fine flow powders were successfully obtained when the molecular weight of PEG was below 6 K and its feed content below 20 wt.%. The ¹H nuclear magnetic resonance (NMR) result indicated the formation of PPDO–PEG–PPDO block structure even in a confined polymerized environment of particles. All the powderous samples contained irregular shaped particles that were observed by scanning electron microscope (SEM). Except for the copolymer with 10 wt.% PEG10K feed content, the mean particle sizes of other powderous samples showed identical values close to 15 μm. This fact was in agreement with the crystallinity of PPDO in the copolymers measured by differential scanning calorimetry (DSC). The water absorption of these copolymers was also measured, and as compared with PPDO homopolymer, the introduction of PEG increased the water absorption of the copolymers. The green and environmentally friendly method disclosed in this work is attractive to directly synthesize biodegradable polymeric particles with potential biomedical applications.     

Comparison of micelles formed by amphiphilic star block copolymers prepared in the presence of a nonmetallic monomer activator

In this article, we describe the synthesis of PEG‐b‐polyester star block copolymers via ring‐opening polymerization (ROP) of ester monomers initiated at the hydroxyl end group of the core poly(ethylene glycol) (PEG) using HCl Et₂O as a monomer activator. The ROP of ε‐caprolactone (CL), trimethylene carbonate (TMC), or 1,4‐dioxan‐2‐one (DO) was performed to synthesize PEG‐b‐polyester star block copolymers with one, two, four, and eight arms. The PEG‐b‐polyester star block copolymers were obtained in quantitative yield, had molecular weights close to the theoretical values calculated from the molar ratio of ester monomers to PEG, and exhibited monomodal GPC curves. The crystallinity of the PEG‐b‐polyester star block copolymers was determined by differential scanning calorimetry and X‐ray diffraction. Copolymers with a higher arm number had a higher tendency toward crystallization. The crystallinity of the PEG‐b‐polyester star block copolymers also depended on the nature of the polyester block. The CMCs of the PEG‐b‐PCL star block copolymers, determined from fluorescence measurements, increased with increasing arm number. The CMCs of the four‐arm star block copolymers with different polyester segments increased in the order 4a‐PEG‐b‐PCL < 4a‐PEG‐b‐PDO < 4a‐PEG‐b‐PLGA < 4a‐PEG‐b‐PTMC, suggesting a relationship between CMC and star block copolymer crystallinity. The partition equilibrium constant, K_v, which is an indicator of the hydrophobicity of the micelles of the PEG‐polyester star block copolymers in aqueous media, increased with decreasing arm number and increasing crystallinity. A key aspect of the present work is that we successfully prepared PEG‐b‐polyester star block copolymers by a metal‐free method. Thus, unlike copolymers synthesized by ROP using a metal as the monomer activator, our copolymers do not contain traces of metals and hence are more suitable for biomedical applications. Moreover, we confirmed that the PEG‐b‐polyester star block copolymers form micelles and hence may be potential hydrophobic drug delivery vehicles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2084–2096, 2008     

Synthesis,micelle formation,and bulk properties of poly(ethylene glycol)‐b‐poly(pentafluorostyrene)‐g‐polyhedral oligomeric silsesquioxane amphiphilic hybrid copolymers

The synthesis, micelle formation, and bulk properties of semifluorinated amphiphilic poly(ethylene glycol)‐b‐poly(pentafluorostyrene)‐g‐cubic polyhedral oligomeric silsesquioxane (PEG‐b‐PPFS‐g‐POSS) hybrid copolymers is reported. The synthesis of amphiphilic PEG‐b‐PPFS block copolymers are achieved using atom transfer radical polymerization (ATRP) at 100 °C in trifluorotoluene using modified poly(ethylene glycol) as a macroinitiator. Subsequently, a proportion of the reactive para‐F functionality on the pentafluorostyrene units was replaced with aminopropylisobutyl POSS through aromatic nucleophilic substitution reactions. The products were fully characterized by ¹H‐NMR and GPC. The products, PEG‐b‐PPFS and PEG‐b‐PPFS‐g‐POSS, were subsequently self‐assembled in aqueous solutions to form micellar structures. The critical micelle concentrations (cmc) were estimated using two different techniques: fluorescence spectroscopy and dynamic light scattering (DLS). The cmc was found to decrease concomitantly with the number of POSS particles grafted per copolymer chain. The hydrodynamic particle sizes (R_h) of the micelles, calculated from DLS data, increase as the number of POSS molecules grafted per copolymer chain increases. For example, R_h increased from ～60 nm for PEG‐b‐PPFS to ～80 nm for PEG‐b‐PPFS‐g‐POSS25 (25 is the average number of POSS particles grafted copolymer chain). Static light scattering (SLS) data confirm that the formation of larger micelles by higher POSS containing copolymers results from higher aggregation numbers (N_agg), caused by increased hydrophobicity. The R_g/R_h values, where R_g is the radius of gyration calculated from SLS data, are consistent with a spherical particle model having a core‐shell structure. Thermal characterization by differential scanning calorimetry (DSC) reveals that the grafted POSS acts as a plasticizer; the glass transition temperature (T_g) of the PPFS block in the copolymer decreases significantly with increasing POSS content. Finally, the rhombohedral crystal structure of POSS in PEG‐b‐PPFS‐g‐POSS was verified by wide angle X‐ray diffraction measurements. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 152–163, 2010     

Synthesis and characterization of graft copolymers of poly(vinyl chloride) with styrene and (meth)acrylates by atom transfer radical polymerization

Graft copolymers of poly(vinyl chloride) with styrene and (meth)acrylates were prepared by atom transfer radical polymerization. Poly(vinyl chloride) containing small amount of pendent chloroacetate units was used as a macroinitiator. The formation of the graft copolymer was confirmed with size exclusion chromatography (SEC), ¹H NMR and IR spectroscopy. The graft copolymers with increasing incorporation of butyl acrylate result in an increase of molecular weight. One glass transition temperature (T_g) was observed for all copolymers. T_g of the copolymer with butyl acrylate decreases with increasing content of butyl acrylate.     

Room‐temperature RAFT copolymerization of 2‐chloroallyl azide with methyl acrylate and versatile applications of the azide copolymers

A new vinyl azide monomer, 2‐chlorallyl azide (CAA), has been synthesized from commercially available reagent in one step. The reversible addition fragmentation chain transfer (RAFT) copolymerization of CAA with methyl acrylate (MA) was carried out at room temperature using a redox initiator, benzoyl peroxide (BPO)/N,N‐dimethylaniline (DMA), in the presence of benzyl 1H‐imidazole‐1‐carbodithioate (BICDT). The polymerization results showed that the process bears the characteristics of controlled/living radical polymerizations, such as the molecular weight increasing linearly with the monomer conversion, the molecular weight distribution being narrow, and a linear relationship existing between ln([M]₀/[M]) and the polymerization time. Chain extension polymerization was performed successfully to prepare block copolymer. Furthermore, the azide copolymers were functionalized by Cu^I‐catalyzed “click” reaction with alkyne‐containing poly(ethylene glycol) (PEG) to yield graft copolymers with hydrophilic PEG side chains. Surface modification of the glass sheet was successfully achieved via the crosslinking reaction of the azide copolymer under UV irradiation at ambient temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1348–1356, 2010     

Effects of composition on the water uptake and hydroplasticisation of the glass transition temperature of methacrylate copolymers

The effects of composition on the glass transition of dry and hydroplasticised copolymers of methyl methacrylate (MMA), butyl methacrylate (BMA) and 2-hydroxypropyl methacrylate (HPMA) were studied by differential scanning calorimetry. Results from the hydroplasticisation studies showed that a high PHPMA content (>75 wt.%) was required for high water absorption and that the amount of water uptake was not linear with HPMA content but increased in an accelerating manner with increasing HPMA content. This behaviour was attributed to the increase in the hydrophilic character of the copolymer due to the strong hydroxyl-hydroxyl interactions at high PHPMA content. The T_gs of the dry copolymers were successfully predicted by all three equations used (rule of mixtures, Fox and Gordon-Taylor) but were poorly predicted for the hydroplasticised copolymers. This failure was attributed to the inadequacy of the equations in accounting for the specific interactions between the different segments of the copolymer chains. HPMA depressed the T_g of the water-saturated copolymers but enhanced the T_g of the dry system and this behaviour has particular relevance to its use in water-based latex paints.     

Determination of Molecular Weight of PDPS Modified Copolymers

Molecular weight (MW) determinations of polydiphenylsiloxane‐co‐polydimethylsiloxane (PDPS/PDMS), polydiphenylsiloxane‐co‐polymethylphenylsiloxane (PDPS/PMPS) and polydiphenylsiloxane‐co‐polymethyl(3,3,3‐trifluoropropyl)siloxane (PDPS/PMFPS) statistical copolymers by gel permeation chromatography (GPC), GPC coupled differential viscometer (GPC‐DV) and light scattering (LS) techniques have been compared and discussed. The MW obtained by GPC‐DV in the PDPS/PDMS and the PDPS/PMPS series agreed with that obtained by LS very well. In PDPS/PDMS copolymers, it was found that the MW obtained by GPC was much lower than that obtained by GPC‐DV and LS, as Ph₂SiO) content is higher than 50 mol%. In PDPS/PMFPS copolymers, the MW obtained by GPC was far different from that obtained by GPC‐DV and the deviation decreased with increasing Ph₂SiO) mol%. The α values of the copolymers can be explained by the structure of the polymer in tetrahydrofuran (THF). Based on the relatively soluble copolymers, not only the differential refractive index increments (dn/dc) of PMPS, PDMS and PMFPS homopolymers but also that of the PDPS homopolymer in THF could be calculated by their corresponding copolymers.     

Copolymerization of styrene and norbornene with β‐diketiminato nickel/methylaluminoxane catalytic system

Styrene–norbornene (S‐N) copolymerizations were carried out using β‐diketiminato nickel complexes CH{C(CF₃)NAr}₂NiBr (Ar = 2,6‐ⁱPr₂C₆H₃, 1 ; Ar = 2,6‐Me₂C₆H₃, 2 ) in the presence of methylaluminoxane. The influence of the comonomer feed content and polymerization temperature on the conversion and composition of the copolymers with the catalytic system was investigated. An increase in the feed ratio of S/N led to an increase in the incorporated styrene content of the resulting copolymer. NMR characterization of the copolymers generated with the catalytic systems showed that the random S‐N copolymers are produced. Differential scanning calorimetric determination of the copolymers shows higher T_g values than polystyrene, and gel permeation chromatographic measurements have shown that the copolymers possess rather narrow molecular weight distributions, suggesting that the copolymerization take place at a single active site. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and properties of copolymers of methyl methacrylate with 2,3,4,5,6‐pentafluoro and 4‐trifluoromethyl 2,3,5,6‐tetrafluoro styrenes: An intrachain interaction between methyl ester and fluoro aromatic moieties

2,3,4,5,6‐Pentafluoro and 4‐trifluoromethyl 2,3,5,6‐tetrafluoro styrenes were readily copolymerized with methyl methacrylate (MMA) by a free radical initiator. The copolymers were soluble in tetrahydrofuran and acetone. The films obtained were transparent and flexible. The glass transition temperatures (T_gs) of the copolymers were found positively deviated from the Gordon–Taylor equation. The positive deviation could be accounted for by dipole–dipole intrachain interaction between the methyl ester group of MMA and the highly fluorinated aromatic moiety, which resulted in a decrease in the segmental mobility of the polymer chains and the enhanced T_g values of the copolymers. The water absorption of PMMA was greatly decreased by copolymerization of MMA with the highly fluorinated styrenes. With as little as 10 mol % of pentafluoro styrene content in the copolymer, the water absorption was decreased to one‐third of that for pure PMMA. The fluorinated styrenes‐MMA copolymers were thermally stable up to 420 °C under air and nitrogen atmospheres. With 50 mol % of MMA in the copolymer, the copolymer was still stable up to 350 °C. Since these copolymers contain a large number of fluorine atoms, the light absorption in the region of the visible to near infrared is decreased in comparison with nonfluorinated polymers. Thus, these copolymers may be suitable for application in optical devices, such as optical fibers and waveguides. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Radiation-induced copolymerization of styrene/n-butyl acrylate in the presence of ultra-fine powdered styrene–butadiene rubber

Styrene (St)/n-butyl acrylate (BA) copolymers were prepared by two-stage polymerization: St/BA was pre-polymerized to a viscous state by bulk polymerization with initiation by benzoyl peroxide (BPO) followed by ⁶⁰Co γ-ray radiation curing. The resultant copolymers had higher molecular weight and narrower molecular weight distribution than conventional methods. After incorporation of ultra-fine powdered styrene–butadiene rubber (UFSBR) with a particle size of 100 nm in the monomer, the glass transition temperature (T_g) of St–BA copolymer increased at low rubber content. Both the St–BA copolymer and the St–BA copolymer/UFSBR composites had good transparency at BA content below 40%.     

Impact of Cationic Charge Density and PEGylated Poly(Amino Acid) Tercopolymer Architecture on Their Use as Gene Delivery Vehicles. Part 2: DNA Protection,Stability, Cytotoxicity,and Transfection Efficiency

The impact of the molecular architecture on the transfection efficiency of PEGylated poly(amino acid) block copolymers was investigated for PEG‐b‐p(l ‐Lys)_x‐b‐p(l ‐Leu)_y, PEG‐b‐p(l ‐Leu)_x‐b‐p(l ‐Lys)_y, and PEG‐b‐p((l ‐Leu)_x‐co‐(l ‐Lys)_y). The block lengths of p(l ‐Lys) and p(l ‐Leu) were varied between 10, 20, and 40; and 10 and 20, respectively, to study the influence of the ionic/hydrophobic balance. The results show that ABC triblock copolymers form smaller and more stable polyplexes with plasmid DNA than AB diblock copolymers—as verified by long‐term aggregation and ethidium bromide exclusion studies—protect the DNA more effectively against nucleases, and provide better transfection efficiencies, as indicated by total protein as well as luciferase expression. More detailed studies revealed that triblock copolymers with p(l ‐Leu) forming the C‐block were most efficient in DNA complexation with a 2.3 times higher transfection rate. Furthermore, increasing the cationic character by increasing the p(l ‐Lys) chain length led to up to 25% higher transfection but at the same time induced some cytotoxicity. Diblock copolymers, where the amino acid–building blocks exist as a random copolymer, bind more loosely with DNA leading to less compact and less stable aggregates with lower transfection efficiencies.     

Controlling the thermomechanical properties of biobased ABA triblock copolymers comprising polylactide (A) and poly(1,2-propylene succinate) (B) with high molecular weight

Bis-hydroxyl-terminated poly(1,2-propylene succinate) (PPS-diols) with high molecular weight (10–40 kDa) are prepared by two-step melt polycondensation of succinic acid and 1,2-propanediol with Ti(BuO)₄ as the catalyst. By using these PPS-diols as macroinitiators, the ring-opening polymerization of d - and l -lactides is readily conducted to obtain enantiomeric ABA triblock copolymers consisting of poly(l -lactide) and PPS (B) (t-l -PPS) as well as those of poly(d -lactide) and PPS (B) (t-d -PPS) which have higher PPS compositions (20–70 wt%) in addition to high molecular weight (20–80 kD). The T_g, T_m, and ΔH_m values of the t-l -PPS copolymers as well as the stereo mixtures of t-l -PPS/t-d -PPS are controlled to linearly decrease with increasing the PPS content. The copolymers also exhibit higher elastomeric properties with increasing the PPS content. The tensile properties of the copolymer films having higher PPS contents (both the single block copolymers and stereo mixtures) are comparable to those of the oil-based thermoplastic elastomers. It is therefore concluded that these block copolymers can afford thermoplastic elastomers or flexible plastic materials having a 100% biobased content.     

Synthesis of poly(ethylene glycol)/polypeptide/poly(D,L‐lactide) copolymers and their nanoparticles

Core‐shell structured nanoparticles of poly(ethylene glycol) (PEG)/polypeptide/poly(D ,L ‐lactide) (PLA) copolymers were prepared and their properties were investigated. The copolymers had a poly(L ‐serine) or poly(L ‐phenylalanine) block as a linker between a hydrophilic PEG and a hydrophobic PLA unit. They formed core‐shell structured nanoparticles, where the polypeptide block resided at the interface between a hydrophilic PEG shell and a hydrophobic PLA core. In the synthesis, poly(ethylene glycol)‐b‐poly(L ‐serine) (PEG‐PSER) was prepared by ring opening polymerization of N‐carboxyanhydride of O‐(tert‐butyl)‐L ‐serine and subsequent removal of tert‐butyl groups. Poly(ethylene glycol)‐b‐poly(L ‐phenylalanine) (PEG‐PPA) was obtained by ring opening polymerization of N‐carboxyanhydride of L ‐phenylalanine. Methoxy‐poly(ethylene glycol)‐amine with a MW of 5000 was used as an initiator for both polymerizations. The polymerization of D ,L ‐lactide by initiation with PEG‐PSER and PEG‐PPA produced a comb‐like copolymer, poly(ethylene glycol)‐b‐[poly(L ‐serine)‐g‐poly(D ,L ‐lactide)] (PEG‐PSER‐PLA) and a linear copolymer, poly(ethylene glycol)‐b‐poly(L ‐phenylalanine)‐b‐poly(D ,L ‐lactide) (PEG‐PPA‐PLA), respectively. The nanoparticles obtained from PEG‐PPA‐PLA showed a negative zeta potential value of ?16.6 mV, while those of PEG‐PSER‐PLA exhibited a positive value of about 19.3 mV. In pH 7.0 phosphate buffer solution at 36 °C, the nanoparticles of PEG/polypeptide/PLA copolymers showed much better stability than those of a linear PEG‐PLA copolymer having a comparable molecular weight. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of ABA-type block copolymer of poly(trimethylene carbonate) with poly(ethylene glycol): Bioerodible copolymer

ABA-type block copolymers of poly(trimethylene carbonate) with poly(ethylene glycol) (M_n 6820), PTMC-b-PEG-b-PTMC, were synthesized by the ring-opening polymerization of 1,3-dioxan-2-one (trimethylene carbonate) in the presence of poly-(ethylene glycol) with stannous octoate catalyst, and the copolymers with various compositions were obtained. The PTMC-b-PEG-b-PTMC copolymers were characterized with Fourier transform infrared and nuclear magnetic resonance spectroscopies. The intrinsic viscosities of resulting copolymers increased with the increase of 1,3-dioxan-2-one content in feed while the molar ratio of monomer over catalyst kept constant. It has been observed that the glass transition temperature (T_g) of the PTMC segments in copolymers, recorded from differential scanning calorimetry, was dependent on the composition of copolymers. The melting temperature (T_m) of PEG blocks in copolymer was lower than that of PEG polymer, and then disappeared as the length of PTMC blocks increased. The results of dynamic contact angle measurement clearly revealed that the hydrophilicity of resulting copolymers increased greatly with the increase of PEG content in copolymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 695–702, 1998