Physical interactions in macroporous scaffolds based on poly(?-caprolactone)/chitosan semi-interpenetrating polymer networks

Polycaprolactone (PCL) and chitosan (CHT) are immiscible polymers. However, biodegradable porous scaffolds of both polymers were obtained by combining different techniques based on the synthesis of semi-interpenetrating polymer networks (SemiIPNs) and melt processing. SemiIPNs were prepared through simultaneous precipitation of the polymer blend (PCL/CHT) and subsequent crosslinking of chitosan with tripolyphosphate (weight fractions of CHT up to 30 wt.%). High porosity PCL/CHT scaffolds with open pore structure and good interconnectivity were obtained. Mechanical properties, evaluated by dynamic-mechanical analysis, decrease as porosity increases. The physical interactions between functional groups of CHT and carbonyl groups of PCL were assessed by FTIR, the shifting of the main relaxation of PCL towards high temperatures as the fraction of CHT increases as well as the evolution of the thermal properties of the system.     

Crystal orientation of poly(?-caprolactone) blocks confined in crystallized polyethylene lamellar morphology of poly(?-caprolactone)-block-polyethylene copolymers

The crystal orientation of poly(?-caprolactone) (PCL) blocks in PCL-block-polyethylene (PE) copolymers has been investigated using two-dimensional small-angle X-ray scattering (2D-SAXS) and 2D wide-angle X-ray diffraction (2D-WAXD) as a function of crystallization temperature T_c and thickness of PCL layers d_PCL. The PCL blocks were spatially confined in the solid lamellar morphology formed by the crystallization of PE blocks (PE lamellar morphology), an alternating structure of crystallized PE lamellae and amorphous PCL layers. This confinement is expected to be intermediate between hard confinement by glassy lamellar microdomains and soft confinement by rubbery ones, because the crystallized PE lamellae consist of hard PE crystals covered with amorphous (or soft) PE blocks. The 2D-SAXS results showed uniaxial orientation of the PE lamellar morphology after applying the rotational shear to the sample. Therefore, it was possible to investigate crystal orientation of PCL blocks within the oriented PE lamellar morphology. The 2D-WAXD results revealed that the c axis of PCL crystals (i.e., stem direction of PCL chains) was parallel to the lamellar surface normal irrespective of T_c when 16.5 nm ≥ d_PCL ≥ 10.7 nm. However, it changed significantly with changing T_c when d_PCL = 8.8 nm; the c axis was perpendicular to the lamellar surface normal at 45 °C ≥ T_c ≥ 25 °C while it was almost random at 20 °C ≥ T_c ≥ 0 °C. These results suggest that the PE lamellar morphology plays a similar role to glassy lamellar microdomains regarding spatial confinement against subsequent PCL crystallization.     

DSC studies of poly(vinyl chloride)/poly(ε-caprolactone)/poly(ε-caprolactone)-b-poly(dimethylsiloxane) blends

Poly(vinyl chloride)/poly(ε-caprolactone)/poly(ε-caprolactone)-b-poly(dimethylsiloxane) [PVC/PCL/(PCL-b-PDMS)] blends were prepared by solvent casting from tetrahydrofuran. The content of PVC was kept constant (60 wt%); the PCL and PCL-b-PDMS contents were varied by replacing different amounts of PCL [0–20 wt% from the PVC/PCL (60/40) blend] with PCL-b-PDMS copolymer having different molecular weights of the PCL blocks. The thermal properties of prepared blends were investigated by differential scanning calorimetry in order to analyse miscibility (through glass transition temperature) and crystallinity. Differential scanning calorimetry analyses show that the PVC/PCL/PCL-b-PDMS blends are multi-phase materials which contain a PVC plasticized with PCL phase, a block copolymer PCL-b-PDMS phase (with crystalline and amorphous PCL and PDMS domains) and a PCL phase (preponderantly crystalline).     

Biodegradable poly(l-lactide)/poly(?-caprolactone)-modified montmorillonite nanocomposites: Preparation and characterization

New nanocomposites were prepared by melt blending poly(l-lactide) (PLLA), poly(?-caprolactone) (PCL), and organically modified montmorillonite (OMMT). The obtained nanocomposites showed enhanced tensile strength, modulus and elongation at break than that of PLLA/PCL blends. The dynamic mechanical analysis showed the increasing mechanical properties with temperature dependence of nanocomposites. Wide-angle X-ray diffraction analysis and transmission electron microscopy indicated that the material formed the nanostructure. Adding OMMT improved the thermal stability and crystalline abilities of nanocomposites. The morphology was investigated by environmental scanning electron microscopy, which showed that increasing content of OMMT reduces the domain size of phase-separated particles. The specific interaction between each polymer and OMMT was characterized by the Flory-Huggins interaction parameter, B, which was determined by the equilibrium melting point depression of nanocomposites. The final values of B showed that PLLA was more compatible with OMMT than PCL.     

Multilayer biopolymer/poly(ε-caprolactone)/polycation nanoparticles

Combining two or more materials for carrier construction is one of the topical approaches to avoid/diminish deficiencies and to increase functionality in delivery systems for bioactive compounds. In this context, here, multilayered nanoparticles comprising both natural (atelocollagen—AteCol; hyaluronic acid derivative—HA) and synthetic [poly(ε-caprolactone)—PCL; polyethylenimine—PEI; poly(l-lysine)—PLL] polymers were prepared and characterized. The combination of a modified double-emulsion method with polymer modification reactions allowed improvement of the polymer particle’s functionality. Fourier transform infrared spectroscopy (FTIR), UV–Vis spectroscopy, fluorescence spectroscopy, dynamic light scattering, transmission/scanning electron microscopy and fluorescence microscopy investigations confirmed the obtention of the envisaged nanomaterials with the expected composition and structure. The double-layered biopolymer/PCL-based nanoparticles formed in a first synthesis step could be successfully coated with PEI and PLL. The gel electrophoresis assay attested the DNA packing ability of the formed nano-vehicles involving surface grafting of the former biopolymer/PCL-based nanoparticles in the case of both cationic polymers, for N/P ratios of 10 (PEI coating) and 3.5 (PLL coating), respectively. According to the FTIR registration, the protein’s native form was preserved. Considering the advantage of biocompatibility and high versatility (controlled size, tuned chemistry and biodegradation rate) some of the resulted nanomaterials may appear as potential candidates for biomedical uses (i.e., drug/gene delivery and tissue engineering).     

The effect of fluorine content on the mechanical properties of poly (?-caprolactone)/nano-fluoridated hydroxyapatite scaffold for bone-tissue engineering

In this study, the effect of fluorine content on the mechanical properties of the novel poly (?-caprolactone)/nano-fluoridated hydroxyapatite nanocomposite scaffolds was investigated. Poly (?-caprolactone)/nano-fluoridated hydroxyapatite (PCL-FHA) scaffolds were produced by solvent casting/particulate leaching method. The fluoridated hydroxyapatite nanopowders had a chemical composition of Ca₁₀(PO₄)₆OH_2−xF_x (where x values were selected equal to 0.5, 1, 1.5 and 2.0). Various weight percentages (10, 20, 30 and 40) of the FHA were added to the PCL. Sodium chloride (NaCl) particles having diameter of 300-500 μm were used as porogen. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) were used to identify the phase structure and functional groups of obtained scaffolds. Mechanical properties of the prepared scaffolds were also determined. Results showed that the compressive strength of scaffolds increases with decreasing the weight percent of fluorine in FHA.     

Kinetics of nucleation and crystallization in poly(?-caprolactone) (PCL)

The recently developed differential fast scanning calorimetry (DFSC) is used for a new look at the crystal growth of poly(?-caprolactone) (PCL) from 185 K, below the glass transition temperature, to 330 K, close to the equilibrium melting temperature. The DFSC allows temperature control of the sample and determination of its heat capacity using heating rates from 50 to 50,000 K/s. The crystal nucleation and crystallization halftimes were determined simultaneously. The obtained halftimes cover a range from 3 × 10⁻² s (nucleation at 215 K) to 3 × 10⁹ s (crystallization at 185 K). After attempting to analyze the experiments with the classical nucleation and growth model, developed for systems consisting of small molecules, a new methodology is described which addresses the specific problems of crystallization of flexible linear macromolecules. The key problems which are attempted to be resolved concern the differences between the structures of the various entities identified and their specific role in the mechanism of growth. The structures range from configurations having practically unmeasurable latent heats of ordering (nuclei) to being clearly-recognizable, ordered species with rather sharp disordering endotherms in the temperature range from the glass transition to equilibrium melting for increasingly perfect and larger crystals. The mechanisms and kinetics of growth involve also a detailed understanding of the interaction with the surrounding rigid-amorphous fraction (RAF) in dependence of crystal size and perfection.     

Effect of fiber diameter on tensile properties of electrospun poly(?-caprolactone)

The tensile properties of electrospun fibers have not been widely investigated due to the difficulties in handling nanofibers and measuring low load for deformation. In this study, the effect of dimensional confinement on free standing biodegradable poly(?-caprolactone) (PCL) is investigated using electrospinning-enabled techniques and a nanoforce tensile tester. The structural properties such as crystallinity and molecular orientation of the spun fibers are examined using wide angle X-ray diffraction (WAXD). The degree of crystallinity and molecular orientation of fibers are enhanced when the diameter of spun fibers is reduced, resulting in improved mechanical strength and stiffness. It is evident that PCL fibers with decreasing fiber diameter exhibit an abrupt shift in tensile performance in comparison to those derived from non-spun systems. The abrupt shift in tensile strength and stiffness of electrospun PCL fibers occurs at around 700 nm in diameter and illustrates the importance of studying the mechanical behavior of the nanofibers, for the first time, systematically with the aid from electrospinning techniques. This shift cannot be otherwise explained by a noticeable change in T_g, and the gradual increase in crystallinity and molecular orientation.     

Poly(acrylic acid)/poly(vinyl alcohol) compositions coaxially electrospun with poly(?-caprolactone) and multi-walled carbon nanotubes to create nanoactuating scaffolds

Skeletal muscle regeneration usually causes scar tissue formation and loss of function, an alternative method is needed. In this study, poly(?-caprolactone), multi-walled carbon nanotubes, and (83/17, 60/40, 50/50, and 40/60) poly(acrylic acid)/poly(vinyl alcohol) (PCL-MWCNT-PAA/PVA) were coaxially electrospun to create scaffolds. All four were conductive; however, not all scaffolds actuated when electrically stimulated. The best response occurred when 20 V was applied. A biocompatibility study where skeletal muscle cells were exposed to 0, 0.14%, and 0.7% MWCNT showed that these concentrations were low enough to not cause harm over a four week period. All scaffolds were biocompatible but, the 40/60 scaffolds had more cells. Fluorescent staining showed large clusters of multinucleated cells with actin interaction. Although scaffold tensile properties are greater than skeletal muscle, our other results show that with more modification to cause contraction instead of bending this combination of materials may show promise as components in an artificial muscle.     

Physical properties of poly(?-caprolactone) coalesced from its α-cyclodextrin inclusion compound

Poly(?-caprolactone) (PCL) is a biodegradable/bioabsorbable polyester used in such biomedical applications as drug delivery and suture manufacturing. PCL has relatively poor physical properties, however, limiting its load-bearing applications. In this work, PCL was processed with α-cyclodextrin (α-CD) to form an inclusion complex (IC). The host α-CD was then stripped away to yield bulk PCL with largely extended, un-entangled polymer chains, a process referred to as coalescence. The changes in thermal, physical, and solid-state rheological properties resulting from this coalescence process were examined. It was found that elongating and un-entangling the PCL chains in this manner resulted in substantial increases in melt-crystallization temperatures, T_cs, up to 25 °C, depending on the cooling rate from the melt. Coalescence also increased the elastic storage modulus, decreased tan δ, increased the average hardness and Young’s modulus by 33 and 53%, respectively, and produced a closer packing of chains in the non-crystalline sample regions, without affecting the overall PCL crystallinity. Interestingly, the reorganized PCL chains in the non-crystalline regions of coalesced samples did not revert to the normal randomly-coiled entangled melt even after heating well above T_m (90 °C) for a month. The addition of small amounts (a few wt%) of coalesced PCL was also found to effectively nucleate the melt-crystallization of as-received PCL. Thus, the semi-crystalline morphology of PCL may be controlled by melt-processing with coalesced PCL added as a nucleant, that is not only necessarily non-toxic and biodegradable/bioabsorbable, but is also chemically compatible.     

Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly(?-caprolactone)-block-poly(2-vinyl pyridine) blends

The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(?-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core-shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases.     

Self-organized thermosets involving epoxy and poly(?-caprolactone)-block-poly(ethylene-co-ethylethylene)-block-poly(?-caprolactone) amphiphilic triblock copolymer

In this work, we investigated the self-assembly behavior of poly(?-caprolactone)-block-poly(ethylene-co-ethylethylene)-block-poly(?-caprolactone) (PCL-b-PEEE-b-PCL) triblock copolymer in epoxy thermosets. The PCL-b-PEEE-b-PCL triblock copolymer was synthesized via the ring-opening polymerization of ?-caprolactone with a hydroxyl-terminated poly(ethylene-co-ethylethylene) as the macromolecular initiator. The hydroxyl-terminated poly(ethylene-co-ethylethylene) was prepared with the hydrogenation reaction of a hydroxyl-terminated polybutadiene. The triblock copolymer was incorporated into the precursors of epoxy to obtain the nanostructured thermosets. It was found that the self-organized nanophases were formed in the mixture before curing reaction and the nanostructures can be further fixed via curing reaction. The self-assembly behavior of the triblock copolymer in epoxy thermosets was investigated by means of atomic force microscopy (AFM), small-angle X-ray scattering (SAXS) and dynamic mechanical thermal analysis (DMTA). Differential scanning calorimetry (DSC) shows that the formation of the self-organized nanophase in the thermosets caused that a part of poly(?-caprolactone) subchains were demixed from epoxy matrix with the occurrence of curing reaction; the fractions of demixed PCL blocks were estimated according to the T_g-composition relation of the model binary blends of epoxy and PCL.     

Effect of the addition of a fugitive salt on electrospinnability of poly(?-caprolactone)

Described in this paper is a novel study focused on producing bead-free ultrafine fibers, with narrow fiber diameter distribution, from Poly(?-caprolactone) (PCL) via electrospinning. High quality product is achieved with the use of a new solvent system that involves an acid-base reaction to produce weak salt complexes, which serve to increase the conductivity of the polymer solution. Additionally, the salt formed dissociates easily and evaporates along with the solvent during the spinning process because its respective acid-base components are volatile at room temperature. This results into the formation of pure PCL nanofibers of ultrafine dimensions. Glacial acetic acid was used as the solvent for the polymer and the organic base pyridine was used to initiate the formation of salt complexes in the solution. Pyridine was added at six different levels to vary the conductivity and examine the latter's effect on fiber morphology. Along with the pyridine content, the polymer concentration was also varied to determine how the two interacted in influencing the size of the fiber and the quality of the structure obtained. It was found that bead-free fibers of sizes lying well within the nano range (140-340 nm) could be produced using the conducting solvent system. Two interesting effects were noted. For a given polymer concentration, the mean fiber diameter increased with increase in pyridine amount. And, lower the polymer concentration, higher was the amount of pyridine required to produce bead-free nanofibers. The combination of these effects along with the fact that the reproducibility of the results was high provided a means of producing fibers with predictable sizes.     

In vitro degradation of poly(l-lactide)/poly(ε-caprolactone) blend reinforced with MWCNTs

The physical and mechanical properties of poly(l-lactide)/poly(??-caprolactone) (PLLA/PCL) blends reinforced with multiwalled carbon nanotubes (MWCNTs) before and after in vitro degradation were investigated. Because of brittleness, PLLA needs to be plasticized by PCL as a soft polymer. The MWCNTs are used to balance the stiffness and the flexibility of PLLA/PCL blends. The results showed that with incremental increase in concentration of MWCNTs in composites, the agglomerate points of MWCNTs were increased. The physical and mechanical properties of prepared PLLA/PCL blends and MWCNT/PLLA/PCL nanocomposites were characterized. The X-ray diffraction analysis of the prepared blends and composites showed that MWCNTs, as heterogeneous nucleation points, increased the lamella size and therefore the crystallinity of PLLA/PCL. The mechanical strength of blends was decreased with incremental increase in PCL weight ratio. The mechanical behavior of composites showed large strain after yielding and high elastic strain characteristics. The tensile tests results showed that the tensile modulus and tensile strength are significantly increased with increasing the concentration of MWCNTs in composites, while, the elongation-at-break was decreased. The in vitro degradation rate of polymer blends in phosphate buffer solution (PBS) increased with higher weight ratio of PCL in the blend. The in vitro degradation rate of nanocomposites in PBS increased about 65% when the concentration of MWCNTs increased up to 3% (by weight). The results showed that the degradation kinetics of nanocomposites for scaffolds can be engineered by varying the contents of MWCNTs.     

Poly(ε-caprolactone)/poly(m-anthranilic acid) and poly(ε-caprolactone)/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) electrospun nanofibers: Characterization,antioxidant, and electrochemical properties

Conducting polymers are widely used in many biomedical applications, but their non-degradability and non-biocompatibility limit their widespread use in applications. For this reason, many studies have been carried out on the developing degradable, biocompatible, and electrically conductive polymers. In this study, mixtures of conductive polymers (poly(m-antranilic acid) (P3ANA) and poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS)) with biocompatible and biodegradable poly(ε-caprolactone) (PCL) were prepared. Their nanofibers were obtained by electrospinning and their antioxidant properties were investigated by 2,2′-azino-bis-3-ethylbenzthiazoline-6-sulfonic acid (ABTS) and copper ion reducing antioxidant capacity (CUPRAC) assays. Electrochemical properties were also investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The highest antioxidant activity was obtained from PCL/P3ANA3 electrospun nanofiber containing 10% (of PCL w/w) P3ANA with 93 and 614 μg TE/mg values for ABTS and CUPRAC assays, respectively. This nanofiber was found to be non-toxic according to 2,5-diphenyl-2H-tetrazolium bromide (MTT) analysis. PCL/PEDOT:PSS electrospun nanofiber has the highest maximum anodic current value of 0.08 mA. The maximum anodic current value of PCL/P3ANA3 nanofiber with the highest amount of P3ANA is also higher than other PCL/P3ANA nanofibers. These nanofibers were characterized by FT-IR, UV–vis., XRD and TGA and their surface morphologies were examined by scanning electron microscopy (SEM).     

Synthesis and self-assembly of a new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymer

New amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by ring-opening polymerization of ε-caprolactone with hydroxy-terminated poly(N-vinylcaprolactam) (PNVCL-OH) as a macroinitiator. The structures of the polymers were confirmed by IR, ¹H NMR and GPC. The critical micelle concentrations of copolymer in aqueous solution measured by the fluorescence probe technique reduced with the increasing of the proportion of hydrophobic parts, so did the diameter and distribution of the micelles determined by dynamic light scattering. The shape observed by transmission electron microscopy (TEM) demonstrated that the micelles are spherical. On the other hand, the UV–vis measurement showed that polymers exhibit a reproducible temperature-responsive behavior with a lower critical solution temperature (LCST). The LCST of PNVCL-OH can be adjusted by controlling the molecular weights, and that of copolymers can be adjusted by controlling the compositions and the concentration. Variable temperature TEM measurements demonstrated that LCST transition was the result of transition of individual micelles to larger aggregates.     

Morphology and mechanical properties of nanostructured blends of epoxy resin with poly(?-caprolactone)-block-poly(butadiene-co-acrylonitrile)-block-poly(?-caprolactone) triblock copolymer

Poly(?-caprolactone)-block-poly(butadiene-co-acrylonitrile)-block-poly(?-caprolactone) triblock copolymer was synthesized via the ring-opening polymerization of ?-caprolactone with dihydroxyl-terminated butadiene-co-acrylonitrile random copolymer. The amphiphilic block copolymer was used to toughen epoxy thermosets via the formation of nanostructures. The morphology of the thermosets was investigated by means of atomic force microscopy, transmission electronic microscopy and small-angle X-ray scattering. It was judged that the formation of the nanostructures in the thermosets follows the mechanism of reaction-induced microphase separation. The thermal and mechanical properties of the nanostructured thermosets were compared to those of the ternary blends composed of epoxy, poly(butadiene-co-acrylonitrile) and poly(?-caprolactone) with the identical content of the modifiers. It is noted that at the same composition the nanostructured thermosets displayed higher glass transition temperatures (T_gs) than the ternary blends, which was evidenced by dynamic mechanical analysis. The fracture toughness of the thermosets was evaluated in terms of the measurement of critical stress field intensity factor (K_1C). It is noted that at the identical composition the nanostructured blends significantly displayed higher fracture toughness than the ternary blends. In addition, the K_1C of the nanostructured thermosets attained the maximum with the content of the modifier less than their counterpart of ternary blending.     

High-pressure solution blending of poly(?-caprolactone) with poly(methyl methacrylate) in acetone + carbon dioxide

The miscibility of blends of poly(?-caprolactone) (PCL, M_w = 14,300) with poly(methyl methacrylate) (PMMA, M_w = 15K or 540K) in acetone + CO₂ mixed solvent has been explored. The liquid-liquid phase boundaries at different temperatures have been determined for mixtures containing 10 wt% total polymer blend, 50 wt% acetone and 40 wt% CO₂. The PCL and PMMA contents of the blends were varied while holding the total polymer concentration at 10 wt%. The polymer blend solutions all displayed LCST-type behavior and required higher pressures than individual polymer components for complete miscibility. Complete miscibilities were achieved at pressures within 40 MPa. The DSC scans show that the blends are microphase-separated. The blends display the melting transition of PCL and the glass transition temperature of the PMMA phases. The presence of PMMA is found to influence the crystallization and melting behavior of PCL in the blends. The DSC results on heat of melting and the FTIR spectra, specifically the changes at 1295 cm⁻¹ band show the changes (decrease) in overall crystallinity of the blend upon addition of PMMA.     

Reversibility of thermodynamic lower critical solution temperature phenomenon in miscible poly(ε-caprolactone)/poly(benzyl methacrylate)

Differential scanning calorimetry and optical microscopy were performed to examine the reversibility of phase separation at above the lower critical solution temperatures in a miscible poly(ε-caprolactone) (PCL)/poly(benzyl methacrylate) (PBzMA) blend system. Upon heating, phase separation occurred via a binodal nucleation and growth (NG) mechanism at above 240 °C, which is a lower critical solution temperature (LCST). The pattern of phase domains suggests that the phase separation was meta-stable. Interestingly, the LCST phase separation was found to be readily reversible to original homogeneity upon cooling at regularly accessible rates. A major factor may be that the temperature window between the LCST curve and blend T_g curve is wide, resulting in a convenient temperature range for the polymer chains to kinetically reorganize to a state favored by the thermodynamic conditions.     

Synthesis and characterization of bioactive molecules grafted on poly(?-caprolactone) by “click” chemistry

A facile and efficient strategy to graft bioactive molecules (nicotinic acid, p-aminobenzoic acid, and phthaloyltryptophan) onto poly(?-caprolactone) (P(?CL)) was achieved by copper-catalyzed Huisgen’s 1,3-dipolar cycloaddition known as click reaction. P(αCl?CL), with 10, 20, and 30% of α-chloro-?-caprolactone (αCl?CL) units were copolymerized by ring opening polymerization using ?CL and αCl?CL as starting materials in the presence of 1,4-butanediol and Sn(Oct)₂. Subsequently, the chloride pendent was converted to azide followed by cycloaddition with terminal alkyne derivatives of the aforementioned bioactive molecules. The complete addition was accomplished at all ratios. The characteristic molecular features of these copolymers were evaluated by FTIR, NMR, and GPC. Thermal analysis data indicated that the grafted compounds led to polymorphic alteration and different pattern of thermal degradation depending on the molecular structure and the size of the grafted compounds. They are the basis for further development of grafted copolymer as drug delivery carriers.