Polyethylene‐poly(L‐lactide) diblock copolymers: Synthesis and compatibilization of poly(L‐lactide)/polyethylene blends

A model polyethylene‐poly(L ‐lactide) diblock copolymer (PE‐b‐PLLA) was synthesized using hydroxyl‐terminated PE (PE‐OH) as a macroinitiator for the ring‐opening polymerization of L ‐lactide. Binary blends, which contained poly(L ‐lactide) (PLLA) and very low‐density polyethylene (LDPE), and ternary blends, which contained PLLA, LDPE, and PE‐b‐PLLA, were prepared by solution blending followed by precipitation and compression molding. Particle size analysis and scanning electron microscopy results showed that the particle size and distribution of the LDPE dispersed in the PLLA matrix was sharply decreased upon the addition of PE‐b‐PLLA. The tensile and Izod impact testing results on the ternary blends showed significantly improved toughness as compared to the PLLA homopolymer or the corresponding PLLA/LDPE binary blends. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2755–2766, 2001     

Effects of functionalized multiwalled carbon nanotubes on the morphologies and mechanical properties of PP/EVA blend

The maleic anhydride‐grafted multiwalled carbon nanotubes (MWCNTs‐g‐MA) have been introduced into polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) blend. To clearly describe the effects of MWCNTs‐g‐MA on the morphology and mechanical properties of PP/EVA blends, the selective distribution of MWCNTs‐g‐MA in the blends is realized through different sample preparation methods, namely, MWCNTs‐g‐MA disperse in EVA phase and MWCNTs‐g‐MA disperse in PP matrix. The results show that the distribution of MWCNTs‐g‐MA has an important effect on the final morphology of EVA and the crystallization structure of PP matrix. Compared with PP/EVA binary blend, distribution of MWCNTs‐g‐MA in PP matrix induces the aggregation of EVA phase at high EVA content and the decrease of spherulite diameters of PP matrix simultaneously. However, when MWCNTs‐g‐MA are dispersed in the EVA phase, they induce more homogeneous distribution of EVA, and the crystallization behavior of PP is slightly affected by MWCNTs‐g‐MA. The corresponding mechanical properties including impact strength and tensile strength are tested and analyzed in the work. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1481–1491, 2009     

Carbon nanotubes induced microstructure and mechanical properties changes in cocontinuous poly( L‐lactide)/ethylene‐co‐vinyl acetate blends

Toughening of poly( L ‐lactide) (PLLA) by elastomer attracts much attention in recent years; however, it is usually associated with the deterioration of modulus and/or strength, resulting in limitation in many applications of the material. In this work, functionalized multiwalled carbon nanotubes (FMWCNTs) were introduced into ethylene‐co‐vinyl acetate toughened PLLA blends. The effects of FMWCNTs content on crystalline structure of PLLA matrix and the morphology of the blends, as well as the selective distribution of FMWCNTs in the ternary nanocomposites were investigated using differential scanning calorimetry (DSC), wide angle X‐ray diffraction, scanning electron microscope, and transmission electron microscope. The results show that FMWCNTs exhibit excellent nucleation role in improving the cold crystallization behaviors of PLLA during the annealing and/or DSC heating processes. The results of mechanical property measurements demonstrate that the modulus, strength, and ductility of the blends can be further improved simultaneously through introducing FMWCNTs. Copyright © 2011 John Wiley & Sons, Ltd.     

Studies on fracture behaviors of immiscible polypropylene/ethylene‐co‐vinyl acetate blends with multiwalled carbon nanotubes

Immiscible polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) blends with two different compositions, one (PP/EVA = 80/20) exhibits the typical sea‐island morphology and the other (PP/EVA = 60/40) exhibits the cocontinuous morphology, were prepared with different contents of f‐MWCNTs. The fracture behaviors, including notched Izod impact fracture and single‐edge notched tensile (SENT) fracture, were comparatively studied to establish the role of f‐MWCNTs in influencing the fracture toughness of PP/EVA blends. Our results showed that, for PP/EVA (80/20) system, f‐MWCNTs do not induce the fracture behavior change apparently. However, for PP/EVA (60/40) system, the fracture toughness of the blend increases dramatically with the increasing of f‐MWCNTs content. More severe plastic deformation accompanied by the fibrillar structure formation was observed during the SENT test. Furthermore, SENT test shows that the significant improvement in fracture toughness of PP/EVA (60/40) with f‐MWCNTs is contributed to the simultaneous enhancement of crack initiation energy and crack propagation energy, but largely dominated by crack propagation stage. Further results based on crystalline structures and morphologies of the blends showed that a so‐called dual‐network structure of EVA and f‐MWCNTs forms in cocontinuous PP/EVA blends, which is thought to be the main reason for the largely improved fracture toughness of the sample. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1331–1344, 2009     

Multi‐walled carbon nanotubes encapsulated with polyurethane and its nanocomposites

Poly(acryloyl chloride) (PACl) was employed to enhance the surface of multi‐walled carbon nanotubes (MWCNTs). MWCNTs were first acid treated to generate hydroxyl groups on the surface, which was reacted with PACl to obtain an encapsulation. The numerous acryloyl chloride groups on the out layer were esterified with a proper amount of ethylene glycol (EG). Subsequently, 4,4′‐methylenebis (phenylisocyanate) (MDI) and 1,4‐butanediol (BDO) were introduced into the system, and a polyurethane (PU) layer was formed in situ. The formation of PU layers on MWCNTs was confirmed by Fourier transform infrared spectrometer (FTIR) and X‐ray photoelectron spectroscope (XPS). The morphology of encapsulated MWCNTs was observed by transmission electron microscope (TEM) and scanning electron microscope (SEM). Thermo gravimetric analysis (TGA) showed the grafted polymer fraction was up to 90%. On introducing the modified MWCNTs into a PU matrix, an increase in tensile strength by 60.6% and improvement in modulus by 6.3% over neat PU was observed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4857–4865, 2008     

Crystallization improvement of poly(L‐lactide) induced by functionalized multiwalled carbon nanotubes

In the present work, the crystalline structures and the melting behaviors of poly(L ‐lactide) (PLLA) obtained after being annealed at different conditions have been investigated through differential scanning calorimetry and wide‐angle X‐ray diffraction, respectively. To improve the crystallization of PLLA, functionalized multiwalled carbon nanotubes (f‐MWCNTs) are introduced into PLLA. Our results show that by prolonging the annealing duration or enhancing the annealing temperature, the degree of crystallinity of PLLA gradually increases. Very important, the addition of f‐MWCNTs promotes the cold‐crystallization of PLLA dramatically even at relatively lower annealing temperature or in shorter annealing duration. Further results show that, whether in neat PLLA or in PLLA/f‐MWCNTs nanocomposite, only α form crystal forms during the annealing process. The glass transition temperature shifts to high temperatures because of the increase of crystallinity. F‐MWCNTs exhibit great heterogeneous nucleation effect for PLLA crystallization through enhancing the nucleation density, leading to homogeneous and tiny spherulites formation in a very short time. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 326–339, 2009     

Synthesis,stereocomplex crystallization and properties of poly(l‐lactide)/four‐armed star poly(d‐lactide) functionalized carbon nanotubes nanocomposites

Functionalized carbon nanotubes (F‐CNTs) were synthesized through the nucleophilic substitution reaction between four‐armed star poly(d ‐lactide) (4PDLA) and acryl chloride of carbon nanotubes and were characterized using Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and thermogravimetric analysis. The results indicated that the 4PDLA was successfully grafted onto carbon nanotubes, and it contained 45.5 wt% of 4PDLA. Poly(l ‐lactide) (PLLA) nanocomposites with different F‐CNTs content were prepared by solution casting. Optical microscopy and scanning electron microscopy results showed that F‐CNTs were uniformly dispersed in the nanocomposites. Crystallization behavior and crystal structure of PLLA nanocomposites were investigated using differential scanning calorimetry, polarizing microscope and X‐ray diffraction. The results found that poly(lactide) stereocomplex crystal could be formed between PLLA and F‐CNTs. F‐CNTs played different roles in the process of solution casting and melting crystallization. Polarizing microscope also revealed that crystallization temperature had a significant effect on the nucleation and spherulites growth of PLLA. Thermal stability and mechanical properties of the nanocomposites were also investigated by thermogravimetric analysis, dynamic mechanical analysis and tensile testing. These results demonstrated that the addition of F‐CNTs obviously improved thermal stability and tensile strength of PLLA. The results showed that PLLA/F‐CNTs would have potential values in engineering fields. Copyright © 2015 John Wiley & Sons, Ltd.     

Morphology and thermal properties of poly(L‐lactide)/poly(butylene succinate‐co‐butylene adipate) compounded with twice functionalized clay

Poly(L ‐lactide) (PLLA)/poly(butylene succinate‐co‐butylene adipate) (PBSA) blends were compounded with Cloisite 25A® (C25A) and C25A functionalized with epoxy groups, respectively. Epoxy groups on the surface of C25A were introduced by treating C25A with (glycidoxypropyl)trimethoxy silane (GPS) to produce so called Twice Functionalized Organoclay (TFC). Variation of morphology and properties of PLLA/PBSA/C25A composites was investigated before and after the treatment with GPS. The morphological structure of the composites was analyzed by using X‐ray diffractometry (XRD) and transmission electron microscopy (TEM). The silicate layers of PLLA/PBSA/TFC were exfoliated to a larger extent than PLLA/PBSA/C25A. Incorporation of the epoxy groups on C25A improved significantly elongation at break as well as tensile modulus and tensile strength of PLLA/PBSA/C25A. The larger amount of exfoliation of the silicate layers in PLLA/PBSA/TFC as compared with that in PLLA/PBSA/C25A was attributed to the increased interfacial interaction between the polyesters and the clay due to chemical reaction. Thermo gravimetric analysis revealed that both T_5%, which was the temperature corresponding to 5% weight loss, and activation energy of thermal decomposition of PLLA/PBSA/TFC were far superior to those of PLLA/PBSA/C25A as well as to those of PLLA/PBSA, indicating that the composites with exfoliated silicate layers were more thermally stable than those with intercalated silicate layers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 478–487, 2005     

Fabrication and characterization of poly(butylene succinate)‐grafted carbon fiber/poly(L‐lactide) nanocomposites

A new poly(butylene succinate) (PBS)‐grafted vapor grown carbon fiber (VGCF)/poly(L ‐lactide) (PLLA) nanocomposites were successfully prepared by an in situ condensation reaction between PBS (M_w = 6,000) and surface oxidized VGCF, followed by direct melt mixing technique, and their mechanical and thermal properties were evaluated. Fourier transform infrared spectroscopy and scanning electron microscopy studies indicate a chemical interaction between the PBS and the surface of VGCF. It was found that the maximum tensile strength and modulus of PBS‐grafted VGCF/PLLA nanocomposites were 135 MPa (27% increase relative to neat PLLA) and 4,400 MPa (29% increase relative to neat PLLA), respectively. The results indicate that significant improvement in the mechanical properties can be accomplished by optimizing the surface modification conditions for VGCF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4433–4441, 2008     

Toughening effect of ethylene‐vinyl acetate rubber on nylon 1010 compatibilized by maleated ethylene‐vinyl acetate copolymers

The toughening effect of ethylene‐vinyl acetate rubbers (EVM) with maleated ethylene‐vinyl acetate copolymers (EVA‐g‐MAH) on the nylon 1010 was investigated. The addition of 5 phr (per hundred nylon 1010) EVM increased the elongation at break of nylon 1010 to a great extent. The notched Izod impact strength of nylon/EVM blends increased with increasing EVM content. Scanning electron microscope showed that the EVM particle size was around 0.5 μm when the EVM content was 5 phr and increased with increasing EVM content. After the addition of EVA‐g‐MAH to nylon/EVM (100/20) blend, the average diameter of EVM particles decreased from more than 1 μm to 0.5–0.6 μm. EVA‐g‐MAH could improve the adhesion between nylon 1010 and EVM. A sharp brittle‐ductile transition (BDT) was observed when the interparticle distance was about 0.2 μm, independent of the addition of EVA‐g‐MAH. The notched Izod impact strength of nylon/EVM blends at low temperatures was measured and the BDT shifted toward low temperatures with increasing EVM or EVA‐g‐MAH content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 434–444, 2009     

The mechanical and electrical properties of carbon nanotube‐grafted polyimide nanocomposites

Polyimide (PI)‐based nanocomposites containing aminophenyl functionalized multiwalled carbon nanotubes (AP‐MWCNTs) obtained through a diazonium salt reaction was successfully prepared by in situ polymerization. PI composites with different loadings of AP‐MWCNTs were fabricated by the thermal conversion of poly(amic acid) (PAA)/AP‐MWCNTs. The mechanical and electrical properties of the AP‐MWCNTs/PI composites were improved compared with those of pure PI due to the homogeneous dispersion of AP‐MWCNTs and the strong interfacial covalent bonds between AP‐MWNTs and the PI matrix. The conductivity of AP‐MWNTs/PI composites (5:95 w/w) was 9.32 × 10^?1 S/cm which was about 10¹⁵ times higher than that of Pure PI. The tensile strength and tensile modules of the AP‐MWCNTs/PI composites with 0.5 wt % of AP‐MWCNTs were increased by about 77% (316.9 ± 10.5 MPa) and 25% (8.30 ± 1.10 GPa) compared to those of pure PI, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 960–966     

Selective distribution,reinforcement, and toughening roles of MWCNTs in immiscible polypropylene/ethylene‐co‐vinyl acetate blends

Polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) nanocomposites with functionalized multiwalled carbon nanotubes (FMWCNTs) have been prepared. The dissolution experiment, transmission electronic microscope, and scanning electronic microscope characterizations prove that, in the nanocomposites with sea–island morphology, although some FMWCNTs are observed in both PP and EVA phases, most of FMWCNTs distribute at the interface; however, in the nanocomposites with cocontinuous morphology, FMWCNTs mainly distribute in EVA phase. Further results based on (differential scanning calorimetry) measurements show that the different dispersion states of FMWCNTs, which are resulted by the different melt blending sequences, result in the different crystallization behaviors of PP matrix. The mechanical measurements show that FMWCNTs exhibit apparent reinforcement and toughening effects for immiscible PP/EVA blends, and such effects are greatly dependent upon the blending sequences. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1882–1892, 2010     

Synthesis and new application of green and recyclable cyclic poly(L‐lactide)‐clay hybrid

We report on the application of biodegradable cyclic poly(L ‐lactide) (PLLA) as new stabilizer; synthesis and application of a cyclic PLLA‐clay hybrid material as recyclable catalyst support. Cyclic PLLAs were used to stabilize palladium nanoparticles synthesized by a wet chemical method. It was found that the palladium particles were smaller with cyclic PLLA stabilizer (～5–10 nm) than the particles obtained from linear PLLA. The cyclic PLLA‐clay hybrid was prepared by a zwitterionic ring‐opening polymerization catalyzed by in situ‐generated N‐heterocyclic carbene catalyst. Palladium (0) nanoparticles were supported and well dispersed on the cyclic PLLA‐clay hybrid to form a new nanocomposite. The nanocomposite was found to be a highly efficient and recyclable catalyst for the aminocarbonylation reactions of aryl halides with various amines. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4167–4174     

Impact fracture toughness of polyamide‐6/montmorillonite nanocomposites toughened with a maleated styrene/ethylene butylene/styrene elastomer

Polyamide‐6 (PA6)/montmorillonite (MMT) nanocomposites toughened with maleated styrene/ethylene butylene/styrene (SEBS‐g‐MA) were prepared via melt compounding. Before melt intercalation, MMT was treated with an organic surfactant agent. Tensile and impact tests revealed that the PA6/4% MMT nanocomposite fractured in a brittle mode. The effects of SEBS‐g‐MA addition on the static tensile and impact properties of PA6/4% MMT were investigated. The results showed that the SEBS‐g‐MA addition improved the tensile ductility and impact strength of the PA6/4% MMT nanocomposite at the expenses of its tensile strength and stiffness. Accordingly, elastomer toughening represents an attractive route to novel characteristics for brittle clay‐reinforced polymer nanocomposites. The essential work of fracture (EWF) approach under impact drop‐weight conditions was used to evaluate the impact fracture toughness of nanocomposites toughened with an elastomer. Impact EWF measurements indicated that the SEBS‐g‐MA addition increased the fracture toughness of the PA6/4% MMT nanocomposite. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 585–595, 2005     

Composites of poly(L‐lactide‐trimethylene carbonate‐glycolide) and surface modified SBA‐15 as bone repair material

This work aims to develop novel composites from a poly(L ‐lactide‐co‐trimethylene carbonate‐co‐glycolide) (PLTG) terpolymer and mesoporous silica (SBA‐15) nanofillers surface modified by post‐synthetic functionalization. SBA‐15 first reacts with a silane coupling agent, γ‐aminopropyl‐trimethoxysilane to introduce ammonium group. PLLA chains were then grafted on the surface of SBA‐15 through ammonium initiated ring‐opening polymerization of L ‐lactide. Composites were prepared via solution mixing of PLTG terpolymer and surface modified SBA‐15. The structures and properties of pure SBA‐15, γ‐aminopropyl‐trimethoxysilane modified SBA‐15 (H₂N‐SBA‐15), PLLA modified SBA‐15 (PLLA‐NH‐SBA‐15), and PLTG/PLLA‐NH‐SBA‐15 composites were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy, N₂ adsorption‐desorption, differential scanning calorimetry, contact angle measurement, and mechanical testing. The results demonstrated that PLLA chains were successfully grafted onto the surface of SBA‐15 with grafting amounts up to 16 wt.%. The PLTG/PLLA‐NH‐SBA‐15 composites exhibit good mechanical properties. The tensile strength, Young's modulus, and elongation at break of the composite containing 5 wt.% of PLLA‐NH‐SBA‐15 were 39.9 MPa, 1.3 GPa, and 273.6%, respectively, which were all higher than those of neat PLTG or of the composite containing 5 wt.% of pure SBA‐15. Cytocompatibility tests showed that the composites present very low cytotoxicity.     

Preparation of poly(styrene‐co‐acrylonitrile)‐grafted multiwalled carbon nanotubes via surface‐initiated atom transfer radical polymerization

The in situ grafting‐from approach via atom transfer radical polymerization was successfully applied to polystyrene, poly(styrene‐co‐acrylonitrile), and polyacrylonitrile grafted onto the convex surfaces of multiwalled carbon nanotubes (MWCNTs) with (2‐hydroxyethyl 2‐bromoisobutyrate) as an initiator. Thermogravimetric analysis showed that effective functionalization was achieved with the grafting approach. The grafted polymers on the MWCNT surface were characterized and confirmed with Fourier transform infrared spectroscopy and nuclear magnetic resonance. Raman and near‐infrared spectroscopy revealed that the grafting of polystyrene, poly(styrene‐co‐acrylonitrile), and polyacrylonitrile slightly affected the side‐wall structures. Field emission scanning electron microscopy showed that the carbon nanotube surface became rough because of the grafting of the polymers. Differential scanning calorimetry results indicated that the polymers grafted onto MWCNTs showed higher glass‐transition temperatures. The polymer‐grafted MWCNTs exhibited relatively good dispersibility in an organic solvent such as tetrahydrofuran. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 460–470, 2007     

Effects of compatibility of poly(l‐lactic‐acid) and thermoplastic polyurethane on mechanical property of blend fiber

Blending poly(l ‐lactic‐acid) (PLLA) and thermoplastic polyurethane (TPU) has been performed in an effort to toughen PLLA without compromising its biodegradability and biocompatibility. The mixing enthalpy calculation of PLLA and TPU predicted that the blend was a thermodynamic miscible system. The viscoelastic properties and phase morphologies of PLLA/TPU blends were investigated further by dynamic mechanical analysis and scanning electron microscopy. It was found that the blend was a partially miscible system. The dynamic mechanical analysis showed that T_g of PLLA and TPU shifted toward with TPU content increasing. Scanning electron microscopy photos showed that the morphologies of the blends changed from a sea island structure to a bicontinuous structure as an increment in TPU content, which suggested that the miscibility of PLLA and TPU was enhanced when the TPU increased. PLLA/TPU blend fibers were fabricated. With the TPU content increasing from 0 wt% to 30 wt%, the tensile strength and initial modulus of blend fibers decreased first then increased, while elongation at break and fracture work gradually increased. The change of tensile properties indicated the toughening effects of TPU on PLLA fibers, also suggested that the formation of blend fibers was influenced by the blend rheological behavior other than the compatibility. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and characterization of poly(L‐lactic acid)–poly(ε‐caprolactone) multiblock copolymers by melt polycondensation

An Erratum has been published for this article in J. Polym. Sci. Part A: Polym. Chem. (2004) 42(22) 5845 New multiblock copolymers derived from poly(L‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL) were prepared with the coupling reaction between PLLA and PCL oligomers with ? NCO terminals. Fourier transform infrared (FTIR), ¹³C NMR, and differential scanning calorimetry (DSC) were used to characterize the copolymers and the results showed that PLLA and PCL were coupled by the reaction between ? NCO groups at the end of the PCL and ? OH (or ? COOH) groups at the end of the PLLA. DSC data indicated that the different compositions of PLLA and PCL had an influence on the thermal and crystallization properties including the glass‐transition temperature (T_g), melting temperature (T_M), crystallizing temperature (T_c), melting enthalpy (ΔH_m), crystallizing enthalpy (ΔH_c), and crystallinity. Gel permeation chromatography (GPC) was employed to study the effect of the composition of PLLA and PCL and reaction time on the molecular weight and the molecular weight distribution of the copolymers. The weight‐average molecular weight of PLLA–PCL multiblock copolymers was up to 180,000 at a composition of 60% PLLA and 40% PCL, whereas that of the homopolymer of PLLA was only 14,000. A polarized optical microscope was used to observe the crystalline morphology of copolymers; the results showed that all polymers exhibited a spherulitic morphology. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5045–5053, 2004     

Synthesis and properties of photocurable biodegradable multiblock copolymers based on poly(ε‐caprolactone) and poly(L‐lactide) segments

Photocurable biodegradable multiblock copolymers were synthesized from poly(ε‐caprolactone) (PCL) diol and poly(L ‐lactide) (PLLA) diol with 4,4′‐(adipoyldioxy)dicinnamic acid (CAC) dichloride as a chain extender derived from adipoyl chloride and 4‐hydroxycinnamic acid, and they were characterized with Fourier transform infrared and ¹H NMR spectroscopy, gel permeation chromatography, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile tests. The copolymers were irradiated with a 400‐W high‐pressure mercury lamp from 30 min to 3 h to form a network structure in the absence of photoinitiators. The gel concentration increased with time, and a concentration of approximately 90% was obtained in 90–180 min for all the films. The photocuring hardly affected the crystallinity and melting temperature of the PCL segments but reduced the crystallinity of the PLLA segments. The mechanical properties, such as the tensile strength, modulus, and elongation, were significantly affected by the copolymer compositions and gel concentrations. Shape‐memory properties were determined with cyclic thermomechanical experiments. The CAC/PCL and CAC/PCL/PLLA (75/25) films photocured for 30–120 min showed good shape‐memory properties with strain fixity rates and recovery rates of approximately 100%. The formation of the network structure and the crystallization and melting of the PCL segments played very important roles for the typical shape‐memory properties. Finally, the degradation characteristics of these copolymers were investigated in a phosphate buffer solution at 37 °C with proteinase‐k and Pseudomonas cepacia lipase. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2426–2439, 2005