Synthesis,characterization, and properties of poly(ester‐phosphoester)s by lanthanum triphenolate‐catalyzed ring‐opening copolymerization

The ring‐opening copolymerization of methyl ethylene phosphate (MEP, 2‐methoxy‐2‐oxo‐1,3,2‐dioxaphospholane) and ε‐caprolactone (CL) was performed in bulk with lanthanum tris(2,6‐di‐tert‐butyl‐4‐methylphenolate)s as single‐component catalyst, resulting in poly(ester‐phosphoester) random copolymers with high molecular weight and moderate molecular weight distribution. The properties of the copolymers were characterized by differential scanning calorimetry, X‐ray diffractometer, dynamic mechanical analysis, and static water contact angle measurement. The crystallinities of the copolymers were reduced with the increase of MEP molar fraction in the products. Moreover, copolymers with enhanced hydrophilicity and lower glass transition temperature could be obtained with higher MEP content, which may provide potential applications in biomedical field. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Synthesis and characterization of biodegradable poly(ester anhydride) based on ε‐caprolactone and adipic anhydride initiated by potassium poly(ethylene glycol)ate

Novel biodegradable poly(ester anhydride) block copolymers based on ε‐caprolactone (ε‐CL) and adipic anhydride (AA) were prepared by sequential polymerization. ε‐CL was first initiated by potassium poly(ethylene glycol)ate and polymerized into active chains (PCL‐O^?K⁺), which were then used to initiate the ring‐opening polymerization of AA. The effects of the AA feed ratio, solvent polarity, monomer concentration, and temperature on sequential polymerization were investigated. The copolymers, obtained under different conditions, were characterized by Fourier transform infrared, ¹H NMR, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The GPC results showed that the weight‐average molecular weights of the block copolymers were approximately 6.0 × 10⁴. The DSC results indicated the immiscibility of the two components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1511–1520, 2003     

Novel synthesis of biodegradable star poly(ethylene glycol)‐block‐poly(lactide) copolymers

Biodegradable star‐shaped poly(ethylene glycol)‐block‐poly(lactide) copolymers were synthesized by ring‐opening polymerization of lactide, using star poly(ethylene glycol) as an initiator and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature. Two series of three‐ and four‐armed PEG‐PLA copolymers were synthesized and characterized by gel permeation chromatography (GPC) as well as ¹H and ¹³C NMR spectroscopy. The polymerization under the used conditions is very fast, yielding copolymers of controlled molecular weight and tailored molecular architecture. The chemical structure of the copolymers investigated by ¹H and ¹³C NMR indicates the formation of block copolymers. The monomodal profile of molecular weight distribution by GPC provided further evidence of controlled and defined star‐shaped copolymers as well as the absence of cyclic oligomeric species. The effects of copolymer composition and lactide stereochemistry on the physical properties were investigated by GPC and differential scanning calorimetry. For the same PLA chain length, the materials obtained in the case of linear copolymers are more viscous, whereas in the case of star copolymer, solid materials are obtained with reduction in their T_g and T_m temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3966–3974, 2007     

Synthesis,characterization, and thermal properties of a novel pentaerythritol‐initiated star‐shaped poly(p‐dioxanone)

A novel star‐shaped poly(p‐dioxanone) was synthesized by the ring‐opening polymerization of p‐dioxanone initiated by pentaerythritol with stannous octoate as a catalyst in bulk. The effect of the molar ratio of the monomer to the initiator on the polymerization was studied. The polymers were characterized with ¹H NMR and ¹³C NMR spectroscopy. The thermal properties of the polymers were investigated with differential scanning calorimetry and thermogravimetric analysis. The novel star‐shaped poly(p‐dioxanone) has a potential use in biomedical materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1245–1251, 2006     

Microwave‐assisted synthesis and characterization of biodegradable block copolyesters based on poly(3‐hydroxyalkanoate)s and poly(D,L‐lactide)

Microwave (MW)‐assisted ring‐opening polymerization (ROP) provides a rapid and straightforward method for engineering a wide array of well‐defined poly(3‐hydroxyalkanoate)‐b‐poly(D,L ‐lactide) (PHA‐b‐PLA) diblock copolymers. On MW irradiation, the bulk ROP of D,L ‐lactide (LA) could be efficiently triggered by a series of monohydroxylated PHA‐based macroinitiators previously produced via acid‐catalyzed methanolysis of corresponding native PHAs, thus affording diblock copolyesters with tunable compositions. The dependence of LA polymerization on temperature, macroinitiator structure, irradiation time, and [LA]₀/[PHA]₀ molar ratio was carefully investigated. It turned out that initiator efficiency values close to 1 associated with conversions ranging from 50 to 85% were obtained only after 5 min at 115 °C. A kinetic investigation of the MW‐assisted ROP of LA gave evidence of its “living”/controlled character under the experimental conditions selected. Structural analyses and thermal properties of biodegradable diblock copolyesters were also performed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

RGD peptide grafted biodegradable amphiphilic triblock copolymer poly(glutamic acid)‐b‐poly(L‐lactide)‐b‐poly(glutamic acid): Synthesis and self‐assembly

A novel amphiphilic biodegradable triblock copolymer (PGL‐PLA‐PGL) with polylactide (PLA) as hydrophobic middle block and poly(glutamic acid) (PGL) as hydrophilic lateral blocks was successfully synthesized by ring‐opening polymerization (ROP) of L ‐lactide (LA) and N‐carboxy anhydride (NCA) consecutively and by subsequent catalytic hydrogenation. The results of cell experiment of PGL‐PLA‐PGL suggested that PGL could improve biocompatibility of polyester obviously. The copolymer could form micelles of spindly shape easily in aqueous solution. The pendant carboxyl groups of the triblock copolymer were further activated with N‐hydroxysuccinimide and combined with a cell‐adhesive peptide GRGDSY. Incorporation of the oligopeptide further enhanced the hydrophilicity and led to formation of spherical micelles. PGL‐PLA‐PGL showed better cell adhesion and spreading ability than pure PLA and the GRGDSY‐containing copolymer exhibited even further improvement in cell adhesion and spreading ability, indicating that the copolymer could find a promising application in drug delivery or tissue engineering. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3218–3230, 2007     

Facile synthesis of ABCDE‐type H‐shaped quintopolymers by combination of ATRP,ROP, and click chemistry and their potential applications as drug carriers

A facile approach to synthesis of ABCDE‐type H‐shaped quintopolymer comprising polystyrene (PSt, C) main chain and poly(ethylene glycol) (PEG, A), poly(ε‐caprolactone) (PCL, B), poly(L ‐lactide) (PLLA, D), and poly(acrylic acid) (PAA, E) side chains was described, and physicochemical properties and potential applications as drug carriers of copolymers obtained were investigated. Azide‐alkyne cycloaddition reaction and hydrolysis were used to synthesize well‐defined H‐shaped quintopolymer. Cytotoxicity studies revealed H‐shaped copolymer aggregates were nontoxic and biocompatible, and drug loading and release properties were affected by macromolecular architecture, chemical composition, and pH value. The release rate of doxorubicin from copolymer aggregates at pH 7.4 was decreased in the order PAA‐b‐PLLA > H‐shaped copolymer > PEG‐PCL‐PSt star, and the release kinetics at lower pH was faster. The H‐shaped copolymer aggregates have a potential as controlled delivery vehicles due to their excellent storage stability, satisfactory drug loading capacity, and pH‐sensitive release rate of doxorubicin. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Cationic ring‐opening polymerization of novel 1,3‐dehydroadamantanes with various alkyl substituents: Synthesis of thermally stable poly(1,3‐adamantane)s

Cationic ring‐opening polymerizations of 5‐alkyl‐ or 5,7‐dialkyl‐1,3‐dehydroadamantanes, such as 5‐hexyl‐ ( 4 ), 5‐octyl‐ ( 5 ), 5‐butyl‐7‐isobutyl‐ ( 6 ), 5‐ethyl‐7‐hexyl‐ ( 7 ), and 5‐butyl‐7‐hexyl‐1,3‐dehydroadamantane ( 8 ), were carried out with super Brønsted acids, such as trifluoromethanesulfonic acid or trifluoromethanesulfonimide in CH₂Cl₂ or n‐heptane. The ring‐opening polymerizations of inverted carbon–carbon bonds in 4–8 proceeded to afford corresponding poly(1,3‐adamantane)s in good to quantitative yields. Poly( 4–8 )s possessing alkyl substituents were soluble in 1,2‐dichlorobenzene, although a nonsubstituted poly(1,3‐adamantane) was not soluble in any organic solvent. In particular, poly( 8 ) exhibited the highest molecular weight at around 7500 g mol^?1 and showed excellent solubility in common organic solvents, such as THF, CHCl₃, benzene, and hexane. The resulting poly( 4–8 )s containing adamantane‐1,3‐diyl linkages showed good thermal stability, and 10% weight loss temperatures (T₁₀) were observed over 400 °C. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4111–4124     

Synthesis and properties of cationic ionomers from poly(ester‐urethane)s based on polylactide

l ‐Lactide (l ‐LA) was polymerized in the presence of N‐methyldiethanolamine as an initiator and Sn(Oct)₂ as a catalyst to give hydroxy‐telechelic poly(l ‐lactide) (PLLA‐diol) bearing a tertiary amine group at the center of the polymer chain. Successive chain extension of the PLLA‐diol with hexamethylene diisocyanate afforded PLLA‐based poly(ester‐urethane)s (PEU) with equally spaced tertiary amine groups. Treatment of the PEU with iodomethane converted tertiary amine groups to quaternary ammonium groups to give cationic ionomers (PEU‐MeI). The thermal, mechanical, hydrophilic, and biodegradation properties of the obtained polymers were investigated. The thermal properties of the PEUs and the PEU‐MeIs were similar each other. The PEU‐MeIs exhibited higher tensile modulus than those of the starting PEUs. The contact angles of water on the PEU‐MeIs were lower than those of the PEUs with similar NMDA content indicating their higher hydrophilicity. In compost degradation tests, the PEU‐MeIs showed slower degradation than those of the PEUs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4423–4428     

New segmented poly(ester‐urethane)s from renewable resources

The physical and mechanical properties of aliphatic homopolyesters from monomers obtainable from renewable resources, namely, 1,3‐propanediol and succinic acid, were improved by their combination with aromatic urethane segments capable of establishing strong intermolecular hydrogen bonds. Segmented poly(ester‐urethane)s were synthesized from dihydroxy‐terminated oligo(propylene succinate)s chain‐extended with 4,4′‐diisophenylmethane diisocyanate. The newly synthesized materials were exhaustively characterized by ¹H NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, dynamic mechanical analysis, and with respect to their main static mechanical properties, an Instron apparatus was used. The average repeat number of the hard segments, evaluated by NMR, ranged from 4 to 9, whereas that of the flexible segments was about 14. The degree of crystallinity, glass‐transition temperature, melting point, tensile strength, elongation, and Young's modulus were influenced by the ratio between hard and soft segments of the segmented copolymer in a predictable way. The results demonstrated that poly(ester‐urethane)s from 1,3‐propanediol and succinic acid are promising thermoplastics. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 630–639, 2001     

Biodegradable photocrosslinkable poly(depsipeptide‐co‐ε‐caprolactone) for tissue engineering: Synthesis,characterization, and In vitro evaluation

Stereolithography has become increasingly popular in scaffold fabrication due to automation and well‐controlled geometry complexity, and consequently, there is a great need for new suitable biodegradable photocrosslinkable polymers. In this study, a new type of photocrosslinkable poly(ester amide) was synthesized based on ε‐caprolactone and l ‐alanine‐derived depsipeptide and was applied to fabrication of three‐dimensional (3D) scaffolds by stereolithography. ¹H nuclear magnetic resonance and Fourier transform infra‐red analysis confirmed the formation of new bonds during the polymer synthesis. Incorporation of depsipeptide increased the glass transition temperature and hydrophilicity of the polymer and accelerated hydrolytic degradation compared with the poly(ε‐caprolactone) homopolymer. The compressive strength of the 3D scaffolds increased with the increasing depsipeptide content. This work demonstrated that incorporation of depsipeptide into photocrosslinkable polyesters resulted in excellent cytocompatibility and tunable degradation rates and mechanical properties and thus expanded the repertoire of biomaterials suitable for 3D photofabrication of high‐resolution tissue engineering scaffolds. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3307–3315     

Air‐stable copper derivatives as efficient catalysts for controlled lactide polymerization: Facile synthesis and characterization of well‐defined benzotriazole phenoxide copper complexes

Air‐stable copper catalysts supported by bis‐ BTP ligands ( BTP = N,O‐bidentate benzotriazole phenoxide) were synthesized and structurally characterized. The reactions of Cu(OAc)₂·H₂O with 2.0 molar equivalents of sterically bulky 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐bis(1‐methyl‐1‐phenylethyl)phenol ( ^CMe2PhBTP ‐H) and 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐di‐tert‐butylphenol ( ^t‐BuBTP ‐H) in refluxing ethanol solution afforded monomeric copper complexes [(^CMe2PhBTP)₂Cu] ( 1 ) and [(^t‐BuBTP)₂Cu] ( 2 ), respectively. The four‐coordinated copper analogue [(^TMClBTP)₂Cu] (3 ) resulted from treatment of 2‐tert‐butyl‐6‐(5‐chloro‐2H‐benzotriazol‐2‐yl)‐4‐methylphenol ( ^TMClBTP ‐H) as the ligand under the same synthetic method with ligand to metal precursor ratio of 2:1, but treatment of complex 3 in acetone gave five‐coordinated monomeric complex [(^TMClBTP)₂Cu(Me₂CO)] (4 ). X‐ray diffraction of single crystals indicates that Cu complex 4 assumes a distorted square pyramidal geometry, penta‐coordinated by two BTP ligands, and one Me₂CO molecule. Catalysis for lactide (LA) polymerization of BTP ‐containing Cu complexes in the presence of various alcohol initiators was investigated. Complex 3 initiated by 9‐anthracenemethanol catalyzes the ring‐opening polymerization effectively not only in a “living” fashion but also in an “immortal” manner, yielding polymers with the predictable molecular weights and narrow molecular weight distributions. Initiations from multifunctional alcohols were able to produce PLLAs with two‐arm linear and three‐arm star‐shaped molecular architectures. The controlled character of Cu complex 3 also enabled us to synthesize the PEG‐b‐PLLA copolymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3840–3849     

Ring‐opening polymerization of rac‐ and meso‐lactide initiated by indium bis(phenolate) isopropoxy complexes

Ring‐opening polymerization of rac‐ and meso‐lactide initiated by indium bis(phenolate) isopropoxides {1,4‐dithiabutanediylbis(4,6‐di‐tert‐butylphenolate)}(isopropoxy)indium ( 1 ) and {1,4‐dithiabutanediylbis(4,6‐di(2‐phenyl‐2‐propyl)phenolate)}(isopropoxy)indium ( 2 ) is found to follow first‐order kinetics for monomer conversion. Activation parameters ΔH^? and ΔS^? suggest an ordered transition state. Initiators 1 and 2 polymerize meso‐lactide faster than rac‐lactide. In general, compound 2 with the more bulky cumyl ortho‐substituents in the phenolate moiety shows higher polymerization activity than 1 with tert‐butyl substituents. meso‐Lactide is polymerized to syndiotactic poly(meso‐lactides) in THF, while polymerization of rac‐lactide in THF gives atactic poly(rac‐lactides) with solvent‐dependent preferences for heterotactic (THF) or isotactic (CH₂Cl₂) sequences. Indium bis(phenolate) compound rac‐(1,2‐cyclohexanedithio‐2,2′‐bis{4,6‐di(2‐phenyl‐2‐propyl)phenolato}(isopropoxy)indium ( 3 ) polymerizes meso‐lactide to give syndiotactic poly(meso‐lactide) with narrow molecular weight distributions and rac‐lactide in THF to give heterotactically enriched poly(rac‐lactides). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4983–4991     

Synthesis of four‐armed poly(ε‐caprolactone)‐block‐poly(ethylene oxide) by diethylzinc catalyst

Biodegradable, amphiphilic, four‐armed poly(?‐caprolactone)‐block‐poly(ethylene oxide) (PCL‐b‐PEO) copolymers were synthesized by ring‐opening polymerization of ethylene oxide in the presence of four‐armed poly(?‐caprolactone) (PCL) with terminal OH groups with diethylzinc (ZnEt₂) as a catalyst. The chemical structure of PCL‐b‐PEO copolymer was confirmed by ¹H NMR and ¹³C NMR. The hydroxyl end groups of the four‐armed PCL were successfully substituted by PEO blocks in the copolymer. The monomodal profile of molecular weight distribution by gel permeation chromatography provided further evidence for the four‐armed architecture of the copolymer. Physicochemical properties of the four‐armed block copolymers differed from their starting four‐armed PCL precursor. The melting points were between those of PCL precursor and linear poly(ethylene glycol). The length of the outer PEO blocks exhibited an obvious effect on the crystallizability of the block copolymer. The degree of swelling of the four‐armed block copolymer increased with PEO length and PEO content. The micelle formation of the four‐armed block copolymer was examined by a fluorescent probe technique, and the existence of the critical micelle concentration (cmc) confirmed the amphiphilic nature of the resulting copolymer. The cmc value increased with increasing PEO length. The absolute cmc values were higher than those for linear amphiphilic block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 950–959, 2004     

Facile synthesis of AB2‐type miktoarm star polymers through the combination of atom transfer radical polymerization and ring‐opening polymerization

A novel miktofunctional initiator ( 1 ), 2‐hydroxyethyl 3‐[(2‐bromopropanoyl)oxy]‐2‐{[(2‐bromopropanoyl)oxy]methyl}‐2‐methyl‐propanoate, possessing one initiating site for ring‐opening polymerization (ROP) and two initiating sites for atom transfer radical polymerization (ATRP), was synthesized in a three‐step reaction sequence. This initiator was first used in the ROP of ?‐caprolactone, and this led to a corresponding polymer with secondary bromide end groups. The obtained poly(?‐caprolactone) (PCL) was then used as a macroinitiator for the ATRP of tert‐butyl acrylate or methyl methacrylate, and this resulted in AB₂‐type PCL–[poly(tert‐butyl acrylate)]₂ or PCL–[poly(methyl methacrylate)]₂ miktoarm star polymers with controlled molecular weights and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.23) via the ROP–ATRP sequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2313–2320, 2004     

Synthesis,functionalization and crosslinking reactions of poly(silylenemethylene)s

Novel poly(silylenemethylene)s have been prepared by the ring‐opening polymerization of 1,3‐disilacyclobutanes followed by a protodesilylation reaction with triflic acid. The silicon–aryl bond cleavage could be controlled by using different leaving groups, for instance phenyl‐ and para‐anisyl substituents. The reactions of the triflate derivatives with organomagnesium compounds, LiAlH₄, amines or alcohols gave functional substituted poly(silylenemethylene)s. Hydrosilylation reactions or reductive coupling with potassium–graphite led to organosilicon network‐polymers, which may serve as suitable precursors for silicon carbide and Si/C/N‐based materials. The structures of the polymers were identified by nuclear magnetic resonance spectroscopy (²⁹Si, ¹³C, ¹H). Copyright © 1999 John Wiley & Sons, Ltd.     

Formation of Silica/Poly(p‐dioxanone) Microspheres by Surface‐Initiated Polymerization

A polymeric film of a biodegradable poly(p‐dioxanone) was grown from 490 nm silica particles by monolayer formation via self‐assembly of hydroxy‐terminated triethoxysilane and subsequent surface‐initiated ring‐opening polymerization of p‐dioxanone. The resulting silica/poly(p‐dioxanone) hybrid particles were characterized by means of ¹H NMR spectroscopy, IR spectroscopy, thermogravimetric analysis, field‐emission scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy.

     

Synthesis and characterization of amphiphilic poly(N‐vinyl pyrrolidone)‐b‐poly(ε‐caprolactone) copolymers by a combination of cobalt‐mediated radical polymerization and ring‐opening polymerization

An amphiphilic block copolymer of poly(N‐vinyl pyrrolidone)‐b‐poly(ε‐caprolactone) (PVP‐b‐PCL) was synthesized by a combination of cobalt‐mediated radical polymerization (CMRP) and ring‐opening polymerization (ROP). The micellar characteristics of this copolymer were subsequently investigated. PVP (M_n = 11,400, M_w/M_n = 1.32) was synthesized at 20 °C via CMRP using a molar ratio of [VP]₀/[V‐70]₀/[Co]₀ = 150/8/1. The PVP was then reacted with 2,2′‐azobis[2‐methyl‐N‐(2‐hydroxyethyl)propionamide] (VA‐086) to modify its cobalt complex chain end to a hydroxyl group. The cobalt (Co) content in the resulting PVP‐OH was 1.2 ppm, indicating that all of the covalent Co? C bonds were cleaved and reacted with VA‐086, and that the separated cobalt complexes were successfully removed. The ROP of CL was subsequently carried out using the produced PVP‐OH as a macroinitiator at 110 °C. The GPC trace of PVP‐b‐PCL was monomodal without any tailing caused by the residual PVP‐OH, indicating that the initiation efficiency was very high. The critical micelle concentration (CMC) of PVP‐b‐PCL (M_n = 18,000, M_w/M_n = 1.35) was 0.015 mg/mL. The PVP‐b‐PCL micelles were spherical in shape with an average diameter of 105 nm. The nanosized PVP‐b‐PCL micelles show promise as novel drug carriers in biomedical and pharmaceutical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3078–3085, 2009     

Well‐defined amphiphilic poly(p‐dioxanone)‐grafted poly(vinyl alcohol) copolymers: Synthesis and micellization

A series of amphiphilic biodegradable and biocompatible poly(p‐dioxanone)‐grafted poly(vinyl alcohol) (PVA) copolymers with well‐defined structure were obtained by a three‐step synthesis based on the “grafting from” concept. The first step (protection step), called the partial silylation of PVA hydroxyl groups, was accomplished by 1,1,1,3,3,3‐hexamethyldisilazane and catalyst chlorotrimethylsilane in dimethyl sulfoxide using THF as cosolvent. The second step was the ring‐opening polymerization of p‐dioxanone (PDO) initiated from the remaining OH groups of the partially silylated PVA. Finally, a deprotection step was followed: the silylether group was deprotected easily under very mild conditions. The synthetic conditions of the first two steps were investigated, and the structures of polymers formed in each step were characterized by various analytical methods. The results showed that the molecular structure of the PVA‐g‐PPDO could be controlled easily by the degree of silylation and the feed ratio. In addition, the micellization of amphiphilic PVA‐g‐PPDO copolymers in water was proved by fluorescence spectra and dynamic light scattering, and the relationship between structural parameters of copolymers and micellar properties was studied preliminarily. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis and characterization of crystalline graft polymer poly(ethylene oxide)‐g‐poly(ɛ‐caprolactone)2 with modulated grafting sites

The graft polymer poly(ethylene oxide)‐g‐poly(?‐caprolactone)₂ (PEO‐g‐PCL₂) with modulated grafting sites was synthesized by the combination of ring‐opening polymerization (ROP) mechanism, efficient Williamson reaction, with thiol–ene addition reaction. First, the precursor of PEO‐Allyl‐PEO with two terminal hydroxyl groups and one middle allyl group was prepared by ROP of EO monomers. Then, the macroinitiator [PEO‐(OH)₂‐PEO]_s was synthesized by sequential Williamson reaction between terminal hydroxyl groups and thiol–ene addition reaction on pendant allyl groups. Finally, the graft polymer PEO‐g‐PCL₂ was obtained by ROP of ?‐CL monomers using [PEO‐(OH)₂‐PEO]_s as macroinitiator. The target graft polymer and all intermediates were well characterized by the measurements of gel permeation chromatography, ¹H NMR, and thermal gravimetric analysis. The crystallization behavior was investigated by the measurements of differential scanning calorimetry, wide‐angle X‐ray diffraction and polarized optical microscope. The results showed that when the PCL content of side chains reached 59.2%, the crystalline structure had been dominated by PCL part and the crystalline structure formed by PEO part can be almost neglected. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2239–2247