Ring‐opening graft polymerization of L‐lactide onto starch granules in an ionic liquid

A room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride ([AMIM]Cl) was a promising direct solvent for starch and nonderivitizing solvent for starch‐effective dissolution, in which the ring‐opening graft polymerization (ROGP) of L ‐lactide (L ‐LA) onto starch chains was carried out homogeneously. The obtained starch grafted poly(L ‐lactide) (starch‐g‐PLLA) was characterized by FTIR, ¹³C NMR, DSC, and WAXD, and the good adhesion between the two components was evidenced by SEM observations although the chains of grafted PLLA were not long. The grafting efficiency of PLLA reached 30% when the ROGP proceeded at 100°C for 10 h with L ‐LA/starch 0.5 : 1 (wt/wt) and stannous octoate (Sn(Oct)₂) as a catalyst, which was calculated according to a standard curve newly created by FTIR method. The homopolymerization of L ‐LA and the disconnection of grafted PLLA from starch‐g‐PLLA were the main competition reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biodegradable amphiphiles of grafted poly(lactide) onto 2‐hydroxyethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers as drug carriers

This article describes the synthesis and characterization of 2‐hydroxylethyl methacrylate‐co‐N‐vinylpyrrolidone copolymers, (HEMA‐co‐NVP), via free radical polymerization followed by grafting of poly(lactide) onto (HEMA‐co‐NVP) copolymers, via ring opening polymerization using tin octoate as a catalyst. The copolymers and the grafted copolymers (i.e., amphiphiles) were subjected to sustained release studies using salicylic acid, as a model drug. Characterization of the formed copolymers was performed using ¹H‐NMR, ¹³C‐NMR, FTIR, TGA, DSC, and SEM techniques. Derivative of TGA thermogram was used to determine %hydrophilicity and %hydrophobicity in the grafted and ungrafted copolymers. The SEM morphology revealed porous layers with crispy structure that were most likely due to the presence of poly(lactide) chains. At lower content of poly(lactide) moiety, grafted copolymers showed non‐Fickian diffusion release rate, whereas Fickian diffusion release rate at higher content of poly(lactide) was observed. The increase of poly(lactide) content (i.e., larger %hydrophobicity) in the copolymer increased the drug‐sustainability, due to the consistent but porous amphiphilic degradable structures that allow controllable release of drug in time interval. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface modification of halloysite nanotubes with l‐lactic acid: An effective route to high‐performance poly(l‐lactide) composites

To improve the interfacial bonding between halloysite nanotubes (HNTs) and poly(l ‐lactide) (PLLA), a simple surface modification of HNTs with l ‐lactic acid via direct condensation polymerization has been developed. Two modified HNTs were obtained: HNTs grafting with l ‐lactic acid (l‐HNTs) and HNTs grafting with poly(l ‐lactide) (p‐HNTs). The structures and properties of l‐HNTs and p‐HNTs were investigated. Then, a series of HNTs/PLLA, l‐HNTs/PLLA and p‐HNTs/PLLA composites were prepared using a solution casting method and were characterized by polarized optical microscopy (POM), field scanning electron microscopy, and tensile testing. Results showed that l ‐lactic acid and PLLA could be easily grafted onto the surface of HNTs by forming an Al carboxylate bond and following with condensation polymerization, and the amounts of the l ‐lactic acid and PLLA grafted on the surface of the HNTs were 5.08 and 14.47%, respectively. The surface‐grafted l ‐lactic acid and PLLA played the important role in improving the interfacial bonding between the nanotubes and matrix. The l‐HNTs and p‐HNTs can disperse more uniformly in and show better compatibility with the PLLA matrix than untreated HNTs. As a result, the l‐HNTs/PLLA and p‐HNTs/PLLA composites had better tensile properties than that of the HNTs/PLLA composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41451.     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

Synthesis of PLLA‐PEOMA comb‐block‐comb type molecular brushes based on AGET ATRP and ring‐opening polymerization

BACKGROUND: Molecular brushes are types of macromolecules with densely grafted side chains on a linear backbone. The synthesis of macromolecular brushes has stimulated much interest due to their great potential in applications in various fields. Poly(L ‐lactide)–poly(ethylene glycol) methyl ether methacrylate (PLLA‐PEOMA) comb‐block‐comb molecular brushes with controlled molecular weights and narrow molecular weight distributions were successfully synthesized based on a combination of activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP) and ring‐opening polymerization. The synthetic route is a combination of the ‘grafting through’ method for AGET ATRP of the PEOMA comb block and the ‘grafting from’ method for the synthesis of the PLLA comb block. Poly(2‐hydroxyethyl methacrylate) (PHEMA) was synthesized by ATRP, and PLLA side chains and PEOMA side chains were grown from the backbones and the terminal sites of PHEMA, respectively. RESULTS: The number‐average degrees of polymerization of PLLA chains and poly[poly(ethylene glycol) methyl ether methacrylate] (PPEOMA) comb blocks were determined using ¹H NMR spectroscopy, and the apparent molecular weights and molecular weight distributions of the brush molecules were measured using gel permeation chromatography. The crystallization of the components in the comb‐block‐comb copolymers was also investigated. The crystallization of PLLA side chains is influenced by PLLA chain length and the content of PPEOMA in the molecular brushes. The comb‐block‐comb copolymer composed of hydrophobic PLLA and hydrophilic PEOMA can self‐assemble into a micellar structure in aqueous solution. CONCLUSION: A combination of AGET ATRP and ring‐opening polymerization is an efficient method to prepare well‐defined comb‐block‐comb molecular brushes. The physical properties of the molecular brushes are closely related to their structures. Copyright © 2009 Society of Chemical Industry     

Preparation,characterization, and drug release behaviors of drug‐loaded ε‐caprolactone/L‐lactide copolymer nanoparticles

Copolymers of ε‐caprolactone and L ‐lactide (PCLLA) with different monomer ratio were synthesized by ring opening polymerization, and drug‐loaded nanoparticles of poly‐ε‐caprolactone (PCL), poly‐L ‐lactide (PLLA), and their copolymers were prepared by precipitation method, respectively. The results of differential scanning calorimetry and X‐ray diffraction indicated that the copolymerization of PCLLA decreased the crystallinity of the polymers, and the results of transmission electron micrograph and laser light scattering (LLS) revealed that the prepared nanoparticles had a spherical shape, and the size of PCLLA nanoparticles (∼ 85 nm) was smaller than that of the PCL and PLLA nanoparticles. The experiment of in vitro drug release showed that the drug release rate from PCLLA nanoparticles was slower than that from PCL and PLLA nanoparticles, and the release profile of PCL6/LA4 nanoparticles appeared to follow zero order kinetics. These results suggested that the polymer composition made a great influence on the nanoparticle size and drug release behavior. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 874–882, 2000     

Effect of dimethyl sulfoxide on synthesis of thermoplastic cellulose‐Graft‐poly(l‐lactide) copolymer using ionic liquid as reaction media

In this study, ring‐opening graft polymerization of l ‐lactide onto cellulose was carried out homogeneously in ionic liquid (IL)/dimethyl sulfoxide (DMSO) co‐solvent as a reaction media. Through the effective control of high viscosity and steric hindrance caused by the interaction between the IL and the hydroxyl group of cellulose by adding DMSO as a co‐solvent, cellulose‐graft‐poly(l ‐lactide) (Cell‐g‐PLLA) copolymer with higher substitution efficiency was successfully prepared, at relatively low concentration of l ‐lactide. The maximum values of molar substitution, degree of lactyl substitution, and degree of polymerization of poly(l ‐lactide) in the copolymer were 3.76, 1.74, and 2.16, respectively, determined by ¹H‐NMR. The prepared cell‐g‐PLLA copolymers showed thermal plasticization with a glass transition temperature of 155°C. In addition, the thermal processibility could be improved as the amount of grafted PLLA in the copolymer increased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41331.     

Synthesis and characterization of AB‐type copolymers poly(L‐lactide)‐block‐poly(methyl methacrylate) via a convenient route combining ROP and ATRP from a dual initiator

Diblock copolymers of poly(L ‐lactide)‐block‐poly(methyl methacrylate) (PLLA‐b‐PMMA) were synthesized through a sequential two‐step strategy, which combines ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP), using a bifunctional initiator, 2,2,2‐trichloroethanol. The trichloro‐terminated poly(L ‐lactide) (PLLA‐Cl) with high molecular weight (M_n,GPC = 1–12 × 10⁴ g/mol) was presynthesized through bulk ROP of L ‐lactide (L ‐LA), initiated by the hydroxyl group of the double‐headed initiator, with tin(II) octoate (Sn(Oct)₂) as catalyst. The second segment of the block copolymer was synthesized by the ATRP of methyl methacrylate (MMA), with PLLA‐Cl as macroinitiator and CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst, and dimethyl sulfoxide (DMSO) was chosen as reaction medium due to the poor solubility of the macroinitiator in conventional solvents at the reaction temperature. The trichloroethoxyl terminal group of the macroinitiator was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy. The comprehensive results from GPC, FTIR, ¹H‐NMR analysis indicate that diblock copolymers PLLA‐b‐PMMA (M_n,GPC = 5–13 × 10⁴ g/mol) with desired molecular composition were obtained by changing the molar ratio of monomer/initiator. DSC, XRD, and TG analyses establish that the crystallization of copolymers is inhibited with the introduction of PMMA segment, which will be beneficial to ameliorating the brittleness, and furthermore, to improving the thermal performance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel comb‐structured‐polymer‐grafted carbon black by surface‐initiated atom transfer radical polymerization and ring‐opening polymerization

Novel comb‐structured‐polymer‐grafted carbon black (CB) was synthesized with a combination of surface‐initiated atom transfer radical polymerization and ring‐opening polymerization. First, poly(2‐hydroxyethyl methacrylate) (PHEMA) was grafted onto the CB surface by surface‐initiated atom transfer radical polymerization. The prepared CB‐g‐PHEMA contained 35.6–71.8% PHEMA, with the percentage depending on the molar ratio of the reagents and the reaction temperature. Then, with PHEMA in CB‐g‐PHEMA as the macroinitiator, poly(?‐caprolactone) (PCL) was grown from the CB‐g‐PHEMA surface by ring‐opening polymerization in the presence of stannous octoate. CB‐g‐PHEMA and CB‐g‐(PHEMA‐g‐PCL) were characterized with Fourier transform infrared, ¹H‐NMR, thermogravimetric analysis, dynamic light scattering, and transmission electron microscopy. The resultant grafted CB had a shell of PHEMA‐g‐PCL. On the whole, the CB nanoparticles were oriented in dendritic lamellae formed by these shells. This hopefully will result in applications in gas sensor materials and nanoparticle patterns. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) graft copolymers and their application as carriers for drug delivery system

Poly(N‐isopropylacrylamide‐co‐hydroxyethyl methacrylate) [P(NIPAM‐co‐HEMA)] copolymer was synthesized by controlled radical polymerization from respective N‐isopropylacrylamide (NIPAM) and hydroxyethyl methacrylate (HEMA) monomers with a predetermined ratio. To prepare the thermosensitive and biodegradable nanoparticles, new thermosensitive graft copolymer, poly(L ‐lactide)‐graft‐poly(N‐isoporylacrylamide‐co‐hydroxyethyl methacrylate) [PLLA‐g‐P(NIPAM‐co‐HEMA)], with the lower critical solution temperature (LCST) near the normal body temperature, was synthesized by ring opening polymerization of L ‐lactide in the presence of P(NIPAM‐co‐HEMA). The amphiphilic property of the graft copolymers was formed by the grafting of the PLLA hydrophobic chains onto the PNIPAM based hydrophilic backbone. Therefore, the graft copolymers can self‐assemble into uniformly spherical micelles ò about 150–240 nm in diameter as observed by the field emission scanning electron microscope and dynamic light scattering. Dexamethasone can be loaded into these nanostructures during dialysis with a relative high loading capacity and its in vitro release depends on temperature. Above the LCST, most of the drugs were released from the drug‐loaded micelles, whereas a large amount of drugs still remains in the micelles after 48 h below the LCST. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Microwave‐irradiated ring‐opening polymerization of D,L‐lactide under atmosphere

Poly(D ,L ‐lactide) (PDLLA) was synthesized by microwave‐irradiated ring‐opening polymerization catalyzed by stannous octoate (Sn(Oct)₂) under atmosphere. The effects of heating medium, monomer purity, catalyst concentration, microwave irradiation time, and vacuum level were discussed. Under the appropriate conditions such as carborundum (SiC) as heating‐medium, 0.15% catalyst, lactide with purity above 99.9%, 450 W microwave power, 30 min irradiation time, and atmosphere, PDLLA with a viscosity–average molecular weight (M_η) over 2.0 × 10⁵ and a yield over 85% was obtained. The dismission of vacuum to ring‐opening polymerization of D ,L ‐lactide (DLLA) under microwave irradiation simplified the process greatly. The temperature under microwave irradiation and conventional heating was compared. The largely enhanced ring‐opening polymerization rate of DLLA under microwave irradiation was the coeffect of thermal effects and microwave effects. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2244–2247, 2006     

Preparation and properties of L‐lactide‐grafted sisal fiber–reinforced poly(lactic acid) composites

Pretreatment of the sisal fiber (SF) grafting with L‐lactide (LA) monomer via a ring‐opening polymerization catalyzed by a Sn(II)‐based catalyst was performed to improve the interfacial adhesion between SF and poly (lactic acid) (PLA). Biocomposites from LA‐grafted SF (SF‐g‐LA) and PLA were prepared by compression molding with fiber weight fraction of 10, 20, 30, and 40%, and then were investigated in contrast with alkali‐treated sisal fiber (ASF) reinforced PLA composites and untreated SF reinforced PLA composites. PLA composites reinforced by half‐and‐half SF‐g‐LA/untreated SF (half SF‐g‐LA) were prepared and studied as well, considering the disadvantages of SF‐g‐LA. The results showed that both the tensile properties and flexural properties of the SF‐g‐LA reinforced PLA composites were improved noticeably as the introduction of SF‐g‐LA, compared with pure PLA, untreated SF reinforced PLA composites and ASF reinforced PLA composites. The mechanical properties of the half SF‐g‐LA reinforced PLA composites were not worse, even better in some aspects, than the SF‐g‐LA reinforced PLA composites. Fourier transform infrared analysis and differential scanning calorimetry analysis exhibited that both the chemical composition and crystal structure of the SFs changed after LA grafting. In addition, the fracture surface morphology of the composites was studied by scanning electron microscopy. The morphological studies demonstrated that a better adhesion between LA‐grafted SF and PLA matrix was achieved. POLYM. COMPOS., 37:802–809, 2016. © 2014 Society of Plastics Engineers     

Synthesis of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) and poly(vinyl alcohol)‐graft‐poly(lactide) in melt with magnesium hydride as catalyst

Grafting of poly(ε‐caprolactone) (PCL) and poly(lactide) (PLA) chains on poly(vinyl alcohol) backbone (PVA degree of hydrolysis 99%) was investigated using MgH₂ environmental catalyst and melt‐grown ring‐opening polymerization (ROP) of ε‐caprolactone (CL) and L ‐lactide (LA), that avoiding undesirable toxic catalyst and solvent. The ability of MgH₂ as catalyst as well as yield of reaction were discussed according to various PVA/CL/MgH₂ and PVA/LA/MgH₂ ratio. PVA‐g‐PCL and PVA‐g‐PLA were characterized by ¹H‐ and ¹³C‐NMR, DSC, SEC, IR. For graft copolymers easily soluble in tetrahydrofuran (THF) or chloroform, wettability and surface energy of cast film varied in relation with the length and number of hydrophobic chains. Aqueous solution of micelle‐like particles was realized by dissolution in THF then addition of water. Critical micelle concentration (CMC) decreased with hydrophobic chains. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The ring‐opening polymerization of D,L‐lactide catalyzed by new complexes of Cu,Zn, Co,and Ni Schiff base derived from salicylidene and L‐aspartic acid

D ,L ‐lactide (LA) was first successfully ring‐opening polymerized in melt by Schiff base complexes K[ML]nH₂O [M = Cu(II), Zn(II), Co(II), Ni(II); n = 2, 2, 3, 3.5; H₃L = L‐aspartic acid‐salicylidene Schiff base], which were prepared by Schiff base ligand derived from salicylidene and L‐aspartic acid and corresponding acetates. The effects of various complexes, the molar ratio of K[ML]nH₂O/LA, the polymerization temperature, and time were studied in detail. The results show that all complexes studied have the ability to initiate the ring‐opening polymerization of D ,L ‐lactide in melt. More than 90% high polymerization conversion and narrow molecular weight distribution (MWD) can be obtained very easily. However, the Ni(II) complex shows better catalytic property than other complexes on the polymerization and the molecular weight (MW) of poly(D ,L ‐lactide) (PLA) produced. With a rise in temperature and a prolongation of time, the MW of PLA decreased remarkably. The MW of PLA prepared by all complexes is not very high, which might be related to the crystalline water of complexes. X‐ray study indicated that PLA produced by Ni(II) complex is an amorphous polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3312–3315, 2002     

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

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

In‐depth characterization of granular starch‐graft‐polyester compositions as obtained by in situ polymerization of lactones from the starch surface

The synthesis of poly(ε‐caprolactone) (PCL)‐grafted granular starch was carried out either in bulk (without solvent) or in toluene suspension by a two‐step procedure. First step relied upon the activation of the hydroxyl groups available at the starch surface by alkylaluminum derivatives like AlEt₃ and removal of non‐surface‐grafted organo‐aluminum active species. The latter species were made free in solution by reaction with the remaining water molecules still contaminating the polymerization medium despite intensive drying of the starch granules. In the second step, ε‐caprolactone was polymerized via a coordination‐insertion ring‐opening polymerization as initiated by the surface‐grafted aluminum alkoxide species. The present contribution aims at investigating various parameters such as nature of the alkyl aluminum activator and monomer (δ‐valerolactone was studied as well), temperature, concentration, and addition of a solvent (polymerization in toluene suspension), reaction time, and also the experimental procedure used to recover the polyester chains and measure the grafting efficiency. It turns out that, under the studied conditions, dialkylaluminum alkoxides surface‐grafted onto the starch granules were more likely generated and promote a fast polymerization reaction with the formation of grafted PCL chains with a molecular weight that can be as high as 225 000 (M_n value) for polymerization carried out in toluene suspension. Copyright © 2004 Society of Chemical Industry     

An investigation of the effect of silane water‐crosslinking on the properties of poly(L‐lactide)

A silane‐grafting water‐crosslinking approach was developed to crosslink poly(L ‐lactide) (PLLA) by grafting vinylalkoxysilane onto PLLA using dicumyl peroxide, followed by silane hydrolysis to form siloxane linkages between PLLA chains. The degree of silane grafting onto PLLA was qualitatively characterized using Fourier transform infrared spectroscopy and quantitatively determined using inductively coupled plasma mass spectrometry. Crosslinked PLLA films were obtained by curing of silane‐grafted PLLA in hot water. Gel fractions were evaluated in order to calculate the crosslinking reaction kinetics and crosslinking density. Various techniques were used to investigate the effect of silane water‐crosslinking on the thermomechanical properties, hydrolysis resistance and biodegradation of PLLA. In addition to an improvement in thermal stability and mechanical properties, hydrolysis resistance was significantly enhanced as a result of silane water‐crosslinking of PLLA. Moreover, the biodegradation of silane water‐crosslinked PLLA was retarded compared with neat PLLA. Copyright © 2010 Society of Chemical Industry     

Enhancing crystallization rate and melt strength of PLLA with four‐arm PLLA grafted silica: The effect of molecular weight of the grafting PLLA chains

To improve the crystallization rate and melt strength of polylactide (PLLA), nano‐size amino silica grafted by four‐arm PLLA (4A‐PLLA) with different molecular weight was synthesized. ¹H nuclear magnetic resonance proved that 4A‐PLLA had been grafted onto the surface of SiO₂ successfully, and the grafting ratios and the degradation behaviors of the grafted SiO₂ nanoparticles (g‐SiO₂) were studied. When the grafted silica was introduced into PLLA matrix, the crystallization rate and melt strength of composites were found to be improved and the length of grafted chain played an important role. The extension rheology indicated that long grafted 4A‐PLLA on the surface of SiO₂ was more efficient in enhancing the elongational viscosity of PLLA, owing to the stronger interactions between the grafted chains and the matrix. The crystallization behavior of ungrafted silica filled composite was similar to that of neat PLA, while g‐SiO₂ played a role of nucleating agent. The crystallinities and the crystallization rates of the composites depended on the content of g‐SiO₂ and the grafted chain length of 4A‐PLLA, especially the latter. Longer grafted chain acted as nucleation site in the matrix and significantly improved the crystallization behaviors of PLLA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45675.     

Synthesis of star‐shaped poly(ε‐caprolactone)‐b‐poly(L‐lactide) copolymers: From star architectures to crystalline morphologies

Hexa‐armed star‐shaped poly(ε‐caprolactone)‐block‐poly(L ‐lactide) (6sPCL‐b‐PLLA) with dipentaerythritol core were synthesized by a two‐step ring‐opening polymerization. GPC and ¹H NMR data demonstrate that the polymerization courses are under control. The molecular weight of 6sPCLs and 6sPCL‐b‐PLLAs increases with increasing molar ratio of monomer to initiator, and the molecular weight distribution is in the range of 1.03–1.10. The investigation of the melting and crystallization demonstrated that the values of crystallization temperature (T_c), melting temperature (T_m), and the degree of crystallinity (X_c) of PLLA blocks are increased with the chain length increase of PLLA in the 6sPCL‐b‐PLLA copolymers. On the contrary, the crystallization of PCL blocks dominates when the chain length of PLLA is too short. According to the results of polarized optical micrographs, both the spherulitic growth rate (G) and the spherulitic morphology are affected by the macromolecular architecture and the length of the block chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface modification of poly‐L‐lactide by photografting of hydrophilic polymers towards improving its hydrophilicity

Poly‐L ‐lactide (PLLA) has been used to prepare scaffolds to guide tissue regeneration in tissue engineering research. However, one of the limitations to the use of PLLA as an ideal biomaterial is its high hydrophobicity. To improve the hydrophilicity of PLLA, hydrophilic polymers were grafted onto PLLA membrane surfaces through the combination of photooxidization in hydrogen peroxide and subsequent ultraviolet (UV)‐induced grafting copolymerization in the monomer solution. Three kinds of modified PLLA membranes (i.e., PLLA‐g‐polyhydroxyethyl methacrylate, PLLA‐g‐polyacrylamide, and PLLA‐g‐polymethacrylic acid) were obtained, resulting in the more wettable PLLA membranes. The occurrence of the grafting polymerization was confirmed by attenuated total reflectance infrared spectroscopy (ATR‐IR) and X‐ray photoelectron spectroscopy (XPS) analysis. Surface morphology of the modified PLLA membranes was studied by scan electronic microscopy (SEM). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2163–2171, 2002