Poly(ɛ‐caprolactone)/polyhedral oligomeric silsesquioxane hybrids: Crystallization behavior and thermal degradation

Biodegradable organic–inorganic hybrids based on poly(?‐caprolactone) (PCL) and polyhedral oligomeric silsesquioxane (POSS) with 5.3–21.3 wt % POSS were synthesized via ring‐opening polymerization (ROP). Chemical structures of the polymers were characterized by proton nuclear magnetic resonance (¹H NMR), fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). X‐ray diffraction (XRD) analysis illustrated that both POSS and PCL segment in POSS/PCL hybrids could crystallize and form two well‐separated crystalline phases except in the one with low content of POSS (5.3 wt %). Melting behavior and non‐isothermal crystallization kinetics of POSS/PCL hybrids were studied by differential scanning calorimeter (DSC). The results indicated that the POSS segment suppressed crystallization of the PCL segment to some extent. Polarizing optical microscope (POM) images showed that POSS/PCL hybrids with the highest POSS loading (21.3 wt %) possessed “snowflake” shape crystals whereas the ones with relatively low POSS loading exhibited classic spherulites. Thermogravimetry (TG) measurement revealed that thermal degradation of POSS/PCL hybrids proceeded by four‐step while PCL homopolymers degraded by a single step. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44113.     

Kinetic and thermodynamic considerations in the synthesis of a new three‐arm poly(ε‐caprolactone)

A new high‐molecular‐weight three‐arm poly(ε‐caprolactone) (PCL) polymer was synthesized in bulk (in the absence of any solvent) by using aluminum tri‐sec butoxide as a tri‐functional initiator. The ring‐opening polymerization of ε‐caprolactone occurs via a coordination‐insertion mechanism that links three growing polyester chains to the Al central atom via metal alkoxide bonds. The global kinetics of the bulk polymerization was determined, and a kinetic model based on monomer‐polymer equilibrium was developed to predict the fractional extent of monomer conversion. Monomer conversions in excess of 95% to form high‐molecular‐weight PCL were achieved. Polym. Eng. Sci. 44:1491–1497, 2004. © 2004 Society of Plastics Engineers.     

Cyclohexene oxide mid‐chain functional macromonomer of poly(ε‐caprolactone): Synthesis,characterization, and photoinitiated cationic homo‐ and copolymerization

In this study, a novel well‐defined epoxy mid‐chain functional macromonomer of poly(ε‐caprolactone) (PCL) has been synthesized by ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) and epoxidation on workup with 3‐chloroperoxybenzoic acid. The ROP of ε‐CL monomer in bulk at 110°C, by means of a dihydroxy functional initiator namely, 3‐cyclohexene‐1,1‐dimethanol in conjunction with stannous‐2‐ethylhexanoate, (Sn(Oct)₂), yielded a well‐defined PCL with a cyclohexene mid‐chain group. The epoxidation of the cyclohexene (CH) mid‐chain group of PCL was performed using 3‐chloroperoxybenzoic acid. GPC, IR, and ¹H‐NMR analyses revealed that a low‐polydispersity macromonomer of PCL with the desired cyclohexene oxide (CHO) functionality at the mid‐chain was obtained. The photoinduced cationic polymerizations of this macromonomer yielded comb‐shaped and graft copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nanocomposites based on poly(ϵ‐caprolactone) and the montmorillonite treated with dibutylamine‐terminated ϵ‐caprolactone oligomer

Dibutylamine‐terminated ε‐caprolactone oligomers (CLOs: CLOL, CLOM, and CLOH) with number–averaged molecular weight (M_n), 500, 1300, and 2200, respectively, were synthesized by the ring‐opening polymerization of ε‐caprolactone initiated by 2‐(dibutylamino)ethanol in the presence of tin(II) 2‐ethylhexanoate. Nanocomposites based on poly(ε‐caploractone) (PCL) and the caprolactone oligomer‐treated montmorillonites (CLO‐Ms: CLOL‐M, CLOM‐M, and CLOH‐M) were prepared by melt intercalation method. The XRD and TEM analyses of the PCL composites revealed that the extent of exfoliation of the clay platelets increased with increasing molecular weight of the used CLOs. Tensile strength and modulus of the PCL/CLO‐M composites increased with increasing molecular weight of the CLO and increasing inorganic content. The tensile modulus of the PCL/CLOH‐M nanocomposite with inorganic content 5.0 wt % was three times higher than that of control PCL. Among the PCL/CLO‐M composites, the PCL/CLOM‐M composite had the highest crystallization temperature and melting temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

Novel biodegradable amphiphilic poly(ε‐caprolactone)/poly(N‐vinylpyrrolidone) blends via successive in situ polymerizations

In this study, biodegradable blends of poly(ε‐caprolactone) (PCL) and poly(N‐vinylpyrrolidone) (PVP) were prepared by a new strategy in the following steps: (1) free radical polymerization of N‐vinyl‐2‐pyrrolidone (NVP) in ε‐caprolactone (CL); (2) ring‐opening polymerization of ε‐caprolactone in the presence of PVP to obtain the target blends. The structure of the blends was confirmed by FTIR and ¹H NMR, and the molecular weight of PCL and PVP were determined by GPC. SEM study revealed that this polymerization method could decrease the disperse phase size and improve the interphase when compared with solution‐blending method. The phase inversion occurred when PVP content was 15–20 wt %. Subsequently, the PCL sphere dispersed in PVP matrix and its size decreased with the increase of PVP content. The contact angle results showed that PVP has a profound effect on hydrophilic properties of PCL/PVP blends. PCL/PVP blends are believed to be promising for drug delivery, cell therapy, and other biomedical applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biodegradable poly(vinyl alcohol)‐graft‐ poly(ε‐caprolactone) comb‐like polyester: Microwave synthesis and its characterization

Poly(vinyl alcohol)‐initiated microwave‐assisted ring opening polymerization of ε‐caprolactone in bulk was investigated, and a series of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) (PVA‐g‐PCL) copolymers were prepared, with the degree of polymerization (DP) of PCL side chains and the degree of substitution (DS) of PVA by PCL being in the range of 3–24 and 0.35–0.89, respectively. The resultant comb‐like PVA‐g‐PCL copolymers were confirmed by means of FTIR, ¹H NMR, and viscometry measurement. The introduction of hydrophilic backbone resulted in the decrease in both melting point and crystallization property of the PVA‐g‐PCL copolymers comparing with linear PCL. With higher microwave power, the DP of PCL side chains and DS of PVA backbone were higher, and the polymerization reaction proceeded more rapidly. Both the DP and monomer conversion increased with irradiation time, while the DS increased first and then remained constant. With initiator in low concentration, the DP and DS were higher, while the monomer was converted more slowly. Microwaves dramatically improved the polymerization reaction in comparison of conventional heating method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3973–3979, 2007     

Polymerization of ϵ‐caprolactone with maleic anhydride: Synthesis and characterization

High‐molecular‐weight polymers of ϵ‐caprolactone (CL) and maleic anhydride (MA) with anhydride group content of about 1% wt have been synthesized and studied. The polymerization reaction was carried out in bulk under nitrogen atmosphere. Stannous octoate (Sn(oct)₂), and 2,2'‐azobisisobutyronitrile (AIBN) were used as a catalyst and an initiator, respectively. A two‐level design of experiments was used to study the effect of various conditions on the characteristics of the copolymer. Reaction time, temperature, and concentration ratio of various reactants (two monomers, monomer to catalyst, and monomer to initiator) were the independent variables used, and the dependent variables included the molecular weight and the anhydride content in the polymer. Nuclear magnetic resonance (NMR) studies indicate that the succinic anhydride units were incorporated individually either to the polymer chain end or backbone. Anhydride content in the polymer and gel permeation chromatograph (GPC) studies indicate that the maleic anhydride acts as the true initiating species rather than as a comonomer in the system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3189–3194, 2000     

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

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

Synthesis,characterization, and hydrolytic degradation of biodegradable poly(ether ester)‐urethane copolymers based on ε‐caprolactone and poly(ethylene glycol)

In this article, a new kind of biodegradable poly(ε‐caprolactone)‐poly(ethylene glycol)‐poly(ε‐caprolactone)‐based polyurethane (PCEC‐U) copolymers were successfully synthesized by melt‐polycondensation method from ε‐caprolactone (ε‐CL), poly(ethylene glycol) (PEG), 1,4‐butanediol (BD), and isophorone diisocyanate (IPDI). The obtained copolymers were characterized by ¹H‐nuclear magnetic resonance (¹H‐NMR), FTIR, and gel permeation chromatography (GPC). Thermal properties of PCEC‐U copolymers were studied by DSC and TGA/DTG under nitrogen atmosphere. Water absorption and hydrolytic degradation behavior of these copolymers were also investigated. Hydrolytic degradation behavior was studied by weight loss method. ¹H‐NMR and GPC were also used to characterize the hydrolytic degradation behavior of PCEC‐U copolymers. The molecular weight of PCL block and PEG block in soft segment and the content of hard segment strongly affected the water absorption and hydrolytic degradation behavior of PCEC‐U copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Microheterogeneous polymer systems prepared by suspension polymerization of methyl methacrylate in the presence of poly(ε‐caprolactone)

Poly(methyl methacrylate) – polycaprolactone (PMMA/PCL) microheterogeneous beads were synthesized by suspension polymerization starting from methyl methacrylate (MMA) monomer and PCL, which was synthesized by ring‐opening polymerization of ε‐caprolactone using ZnCl₂ as initiator. The resulting polymer was fully characterized by ¹H and ¹³C NMR, differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and dynamic mechanical thermal analysis (DMTA). The size distribution and morphology of the resulting beads were investigated by optical microscopy and scanning electron microscopy (SEM). Moreover, blends of PMMA beads and PCL in different proportions were prepared and the morphology of the films was examined by optical microscopy. The low compatibility between PMMA and PCL was clearly evidenced through these experiments.     

Fast and efficient synthesis of high molecular weight poly(epsilon‐caprolactone) diols by microwave‐assisted polymer synthesis

Because of advantageous features such as shorter reaction times, greater yields, limited generation of by‐products and relatively easy and straightforward scale‐up, microwave‐assisted synthesis has become a very appealing tool in organic synthesis. Conversely, its implementation in the context of the synthesis of biomaterials for biopharmaceutical applications has been more limited. The present work reports on the fast and efficient microwave‐assisted synthesis of poly(ethylene glycol) (PEG)‐initiated poly(ε‐caprolactone) diols (PCL) by the ring‐opening polymerization (ROP) of ε‐caprolactone using stannous octanoate as catalyst. Since the PEG content in the synthesized copolymers was extremely low (0.2–1.9%), products were highly hydrophobic and displayed the intrinsic thermal properties of pure PCL. As opposed to the more time‐consuming conventional thermally‐driven synthesis that usually demands 2–3 h, the microwave technique resulted in intermediate to high molecular weight PEG‐PCL derivatives within 10–15 min. The influence of different parameters affecting the synthetic process, namely monomer‐to‐initiator ratio, reaction time, catalyst concentration and the presence, type, and concentration of solvent were thoroughly investigated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and mechanical properties of poly(ε‐caprolactone)/polyhedral oligomeric silsesquioxane nanocomposites

Poly(ε‐caprolactone) (PCL)/trisilanolphenyl polyhedral oligomeric silsesquioxane (TspPOSS) nanocomposites were prepared by solution mixing followed by film casting. Wide‐angle X‐ray diffraction and field‐emission scanning electron microscopy observations showed that the POSS molecules formed crystal domains and dispersed uniformly on the nanoscale in the PCL matrix. Fourier transform infrared analysis of the nanocomposites revealed that there are hydrogen‐bonded interactions between the silanol group of the TspPOSS and carbonyl oxygen of the PCL. Differential scanning calorimetry, tensile testing, and dynamic mechanical analysis (DMA) showed that, with increasing POSS content in the nanocomposites, the melting temperature and degree of crystallinity decreased while glass transition temperature, tensile modulus and strength increased without sacrificing the ductility of the PCL. DMA results also demonstrated the presence of a rubbery plateau above the melting temperature of the PCL/TspPOSS nanocomposites, and the moduli at the plateau region increased with increasing POSS content in the nanocomposites, implying that the PCL/TspPOSS nanocomposites formed a physically crosslinked structure. The physically crosslinked PCL/TspPOSS nanocomposites exhibited a thermally triggered shape memory effect. Copyright © 2012 Society of Chemical Industry     

Three‐arm poly (ε‐caprolactone) by extrusion polymerization

Three‐arm poly (ε‐caprolactone, reactive extruded) (REX‐PCL) polymer was continuously produced using a twin‐screw extruder with aluminum tri‐sec butoxide (ATSB) initiator in residence times of less than five minutes. Monomer conversions in excess of 95% were achieved, and high molecular weight PCL was produced. The number average molecular weight of each arm of REX‐PCL ranged from 30,000 to 200,000 g/mol. A screw configuration comprising entirely of conveying elements was most effective in the extrusion polymerization process. The REX‐PCL polymer was characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and intrinsic viscosity measurements. POLYM. ENG. SCI. 46:235–240, 2006. © 2006 Society of Plastics Engineers     

Ring‐opening polymerization of ε‐caprolactone with a divalent samarium bis(phosphido) complex

The ring‐opening polymerization of ε‐caprolactone initiated with a divalent samarium bis(phosphido) complex [Sm(PPh₂)₂] is reported. The polymerization proceeded under mild reaction conditions and resulted in polyesters with number‐average molecular weights of 8.2 × 10³ to 12.5 × 10³. The yield and molecular weight of poly(ε‐caprolactone)s were dependent on the experimental parameters, such as the monomer/initiator molar ratio, the monomer concentration, the reaction temperature, and the polymerization time. The obtained polymers were characterized with Fourier transform infrared, NMR, gel permeation chromatography, and differential scanning calorimetry. On the basis of an end‐group analysis of low‐molecular‐weight polymers by NMR spectroscopy, a coordination–insertion mechanism is proposed for the polymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1558–1564, 2005     

Ring‐opening polymerization of trimethylenecarbonate and its copolymerization with ϵ‐caprolactone by lanthanide (II) aryloxide complexes

Lanthanide metal (II) 2,6‐di‐tert‐butylphenoxide complexes (ArO)₂Ln(THF)₃ (Ln = Sm 1 , Yb 2 ) alone have been developed to catalyze the ring‐opening polymerization of trimethylenecarbonate (TMC) and random copolymerization of TMC and ε‐caprolactone (ε‐CL) for the first time. The influence of reaction conditions, such as initiator, initiator concentration, polymerization temperature, and polymerization time, on monomer conversion, molecular weight, and molecular weight distribution of the resulting PTMC was investigated. It was found that the divalent complex 1 showed higher activity for the polymerization of TMC than complex 2 . The random structure and thermal behavior of the copolymers P(TMC‐co‐CL) have been characterized by ¹H NMR, ¹³C NMR, GPC, and DSC analysis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Asymmetric penta‐armed poly(ε‐caprolactone)s with short‐chain phosphazene core: synthesis,characterization, and in vitro degradation

A novel hydroxyl‐terminated short‐chain penta‐armed phosphazene was prepared. This penta‐armed compound was studied as an initiator for the synthesis of asymmetric penta‐armed poly(ε‐caprolactone)s in the presence of stannous octoate. The effect of molar ratio of monomer to initiator was investigated. Thermal analysis revealed that the penta‐armed poly(ε‐caprolactone)s possessed lower melting point and crystallinity than linear ones. The penta‐armed poly(ε‐caprolactone)s with long chain‐length exhibited higher onset decomposition temperature and maximum decomposition temperature than linear ones owing to the presence of the phosphazene core. The in vitro degradation of linear and penta‐armed PCL was performed in phosphate buffer solution at 37 and 55 °C. Copyright © 2005 Society of Chemical Industry     

Synthesis and characterization of novel lipid functionalized poly(ε‐caprolactone)s

A series of novel lipid functionalized poly(ε‐caprolactone)s (PCLs) were synthesized through ROP of ε‐caprolactone in the presence of threo‐9,10‐dihydroxyoctadecanoic acid, synthesized from oleic acid. PCLs with different molecular weights were obtained by controlling the molar ratio of the initiator to the monomer. DSC and XRD analysis indicate that the crystallinity of PCLs decreased when compared to unfunctionalized PCL. The enzymatic degradation study shows that for samples with lower lipid derivatives content, a higher enzymatic degradation rate was observed because the lipase enzymes attack the ester bonds of the polymer; increased lipid content therefore inhibits the action of the lipase enzymes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(ϵ‐caprolactone)‐functionalized carbon nanofibers by surface‐initiated ring‐opening polymerization

Carbon nanofibers (CNFs) were covalently functionalized with biodegradable poly(?‐caprolactone) (PCL) by in situ ring‐opening polymerization (ROP) of ?‐caprolactone in the presence of stannous octoate. Surface oxidation treatment of the pristine CNFs afforded carboxylic CNFs (CNF‐COOH). Reaction of CNF‐COOH with excess thionyl chloride (SOCl₂) and glycol produced hydroxyl‐functionalized CNFs (CNF‐OH). Using CNF‐OH as macroinitiator, PCL was covalently grafted from the surfaces of CNFs by ROP, in either the presence or absence of sacrificial initiator, butanol. The grafted PCL content was achieved as high as 64.2 wt %, and can be controlled to some extent by adjusting the feed ratio of monomer to CNF‐OH. The resulting products were characterized by FTIR, NMR, Raman spectroscopy, TGA, DSC, SEM, TEM, HRTEM, and XRD. Core–shell nanostructures were observed under HRTEM for the PCL‐functionalized CNFs because of the thorough grafting. The PCL‐grafted CNFs showed different melting and crystallization behaviors from the mechanical mixture of PCL and CNF‐OH. This approach to PCL‐functionalized CNFs opens an avenue for the synthesis, modification, and application of CNF‐based nanomaterials and biomaterials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007