Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs...Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of α-CD.展开更多
In the absence of catalyst,70%hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid(PSA).Then PSA was applied to synthesis ofε-caprolactone(ε-CL)by oxidation of cyclohexanone in t...In the absence of catalyst,70%hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid(PSA).Then PSA was applied to synthesis ofε-caprolactone(ε-CL)by oxidation of cyclohexanone in the heterogeneous system.In order to achieve material recycle,solid precipitated in the process of synthesizingε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride,which was characterized by IR(infrared spectra)and1HNMR(1H nuclear magnetic resonance).Effects of molar ratio of PSA to cyclohexanone,acetic acid dosage,reaction temperature,reaction time on conversion of cyclohexanone,yield and selectivity ofε-CL were investigated respectively.The results indicated that conversion of cyclohexanone,yield and selectivity ofε-CL were upto 98.1%,97.5%and 99.4%respectively under the optimal conditions.In addition,in the process of synthesizing succinic anhydride,the optimal yield of succinic anhydride reached 67.4%.展开更多
Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composit...Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composite with the optimum concentration of 45 wt% LiTFSI and 75 wt% Li1.5Al0.5Ge1.5(PO4)3(LAGP,NASICON-type structure) exhibits a high ionic conductivity(σi=0.17 mS cm-1) at 30℃,a transference number of 0.30,and is stable up to 5.0 V.The composite electrolyte is a flexible and self-standing membrane.Solid-state LiFePO4//Li batteries with this composite electrolyte demonstrate excellent cycling stability with high discharge capacity of 157 mA h g-1,high capacity retention of 96% and coulombic efficiency of 98.5% after 130 cycles at 30℃ and 0.1 C rate.These electrochemical properties are better than other PCL-based allsolid-lithium batteries,and validate the concept of "polymer-in-ceramic" by avoiding the drawback of lower conductivity in prior "polymer-in-ceramic" electrolyte at high concentration of the ceramic.展开更多
Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst f...Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst for the first time. The influences of different rare earth elements, monomer and catalyst concentration as well as reaction time on the polymerization were investigated. Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.展开更多
The mechanical properties and water solubility of electrospinning SF films limit their use as biomaterials. In order to develop a tissue engineering biomaterial with both satisfying biological properties and sufficien...The mechanical properties and water solubility of electrospinning SF films limit their use as biomaterials. In order to develop a tissue engineering biomaterial with both satisfying biological properties and sufficient biomechanical properties,blended films composed of silk fibroin( SF) and poly( ε-caprolactone)( PCL) were fabricated by electrospinning in this study. Scanning electron microscope( SEM), X-ray diffraction( XRD),thermal analysis,Fourier transform-infrared( FT-IR),Raman spectra,mechanical testing,and water solubility were used to characterize the morphological, structural and mechanical properties of the blended electrospinning films. Results showed that the diameter of the blended fiber was distributed between 600 and1000 nm,and the fiber diameter increased as the PCL content increased. There is no obvious phase separation due to the similarity and intermiscibility,as well as the interactions( mainly hydrogen bonds), between the two polymers. Meanwhile, the secondary structures of SF changed from random coils and Silk I to Silk II because of the interactions between SF and PCL. For this reason,the tensile strength and elongation at break of the electrospinning films improved significantly,and the water solubility decreased. In conclusion,the blended electrospinning films fabricated in this study showed satisfying mechanical properties and water insolubilities,and they may be promising biomaterials for applications in tissue engineering for blood vessels,nerve conduits,tendons,ligaments and other tissues.展开更多
Recent studies have shown the potential of artificially synthesized conduits in the repair of peripheral nerve injury. Natural biopolymers have received much attention because of their biocompatibility. To investigate...Recent studies have shown the potential of artificially synthesized conduits in the repair of peripheral nerve injury. Natural biopolymers have received much attention because of their biocompatibility. To investigate the effects of novel electrospun absorbable poly(ε-caprolactone)/type Ⅰ collagen nanofiber conduits(biopolymer nanofiber conduits) on the repair of peripheral nerve injury, we bridged 10-mm-long sciatic nerve defects with electrospun absorbable biopolymer nanofiber conduits, poly(ε-caprolactone) or silicone conduits in Sprague-Dawley rats. Rat neurologica1 function was weekly evaluated using sciatic function index within8 weeks after repair. Eight weeks after repair, sciatic nerve myelin sheaths and axon morphology were observed by osmium tetroxide staining, hematoxylin-eosin staining, and transmission electron microscopy.S-100(Schwann cell marker) and CD4(inflammatory marker) immunoreactivities in sciatic nerve were detected by immunohistochemistry. In rats subjected to repair with electrospun absorbable biopolymer nanofiber conduits, no serious inflammatory reactions were observed in rat hind limbs, the morphology of myelin sheaths in the injured sciatic nerve was close to normal. CD4 immunoreactivity was obviously weaker in rats subjected to repair with electrospun absorbable biopolymer nanofiber conduits than in those subjected to repair with poly(ε-caprolactone) or silicone. Rats subjected to repair with electrospun absorbable biopolymer nanofiber conduits tended to have greater sciatic nerve function recovery than those receiving poly(ε-caprolactone) or silicone repair. These results suggest that electrospun absorbable poly(ε-caprolactone)/type Ⅰ collagen nanofiber conduits have the potential of repairing sciatic nerve defects and exhibit good biocompatibility. All experimental procedures were approved by Institutional Animal Care and Use Committee of Taichung Veteran General Hospital, Taiwan, China(La-1031218) on October 2, 2014.展开更多
Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through s...Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition： [ε-caprolactone]：[catalyst] = 600, 56 ℃, toluene： 2 ml, poly（ε-caprolactone） （PCL） with Mw = 11,2782 and PDI = 1.96 was achieved.展开更多
In this study a low molecular weight triblock copolymer derived fromε-caprolactone and tetrahydrofuran was used as a non-reactive compatibilizer of immiscible PLA/PCL blends.Ternary blends with 0,1.5 wt%,3 wt%and 5 w...In this study a low molecular weight triblock copolymer derived fromε-caprolactone and tetrahydrofuran was used as a non-reactive compatibilizer of immiscible PLA/PCL blends.Ternary blends with 0,1.5 wt%,3 wt%and 5 wt% copolymer and about 75 wt%PLA were prepared by single screw extrusion and characterized by scanning electron microscopy(SEM),differential scanning calorimetry(DSC),dynamic mechanical analysis(DMA),tensile and Izod impact testing.SEM micrographs showed that the size of the dispersed PCL domains was practically constant regardless of copolymer concentration.This result can be explained by the low shear rate employed during processing step and a decrease of PCL viscosity by presence of the triblock copolymer.However,when the copolymer concentration increased,strain at break of PLA/PCL blends also increased.PLA/PCL blend with 0 wt% copolymer presented 2%strain at break,whereas PLA/PCL blend with 5 wt%copolymer exhibited 90%.展开更多
Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was fou...Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found thatthe equilibrium melting points (T_m^0) of PCL samples depend on their molecular weights. Wide angle X-ray diffractionmeasurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were moreperfect than those of the low molecular weigh ones. These results demonstrate that the concentration of the end groups ofPCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (ΔH_u) wasdetermined to be 11.3 kJ/mol for PCL.展开更多
An aromatic heterocyclic Schiff base neodymium complex bearing thiazole was synthesized and its activity in the ring-opening polymerization ofε-caprolactone(CL)was examined.The conditions of the CL/Nd molar ratio,mon...An aromatic heterocyclic Schiff base neodymium complex bearing thiazole was synthesized and its activity in the ring-opening polymerization ofε-caprolactone(CL)was examined.The conditions of the CL/Nd molar ratio,monomer concentration,polymerization time and temperature were investigated.Activities of ca.171 kg/Nd·h were obtained under the optimum condition(CL/Nd=1600(molar ratio),[CL]=2.26 mol L^(-1),1 h at 50℃),giving a poly(ε-caprolactone)(PCL)of number-average molecular weight M_n=5.4×10~4 and molecular...展开更多
The ideal small-diameter vascular grafts should mimic the nanostructure and mechanical properties of nature blood vessel. In this study, electrospun chitosan( CS)/poly( L-lactic-co-ε-caprolactone)( PLCL) nanofibers w...The ideal small-diameter vascular grafts should mimic the nanostructure and mechanical properties of nature blood vessel. In this study, electrospun chitosan( CS)/poly( L-lactic-co-ε-caprolactone)( PLCL) nanofibers were developed for potential small-diameter blood vessel applications. CS is a positively charged polymer which is beneficial for cell attachment and growth,while PLCL provides favorable mechanical support due to its excellent elasticity. Typical nanofibrous structure was observed in both CS/PLCL and pure PLCL scaffolds. The optimal mechanical property could be achieved when the weight ratio of CS/PLCL was 1 ∶ 2.Compared with pure PLCL scaffolds, the CS/PLCL scaffolds showed higher hydrophilicity and markedly promoted the attachment,spreading and proliferation of human umbilical vein endothelial cells( HUVECs). Hence,CS/PLCL scaffolds can be used as potential vascular grafts.展开更多
Block copolyesters of L-lactide and ε-caprolactone were synthesized by melt copolymerization of ε-caprolactone and L-lactide.The degradation performance of copolyesters was investigated by quartz crystal microbalanc...Block copolyesters of L-lactide and ε-caprolactone were synthesized by melt copolymerization of ε-caprolactone and L-lactide.The degradation performance of copolyesters was investigated by quartz crystal microbalance with dissipation(QCM-D).Diisocyanate terminated copolyesters could obtain via the reaction of copolyesters and diisocyanate.Diisocyanate terminated copolyesters could react with polyol resin to prepare degradable polyurethane which can be used in antifouling coatings.In this paper,we also discussed the degradation products release action and antifouling performance of the copolyesters film.展开更多
A series of random and block poly（ L-lactide-co-e-caprolactone ） （ PCLA ） copolymers whh different composition are prepared using stannous octaoate as catalyst.The effects of the amount of initiator on the intrins...A series of random and block poly（ L-lactide-co-e-caprolactone ） （ PCLA ） copolymers whh different composition are prepared using stannous octaoate as catalyst.The effects of the amount of initiator on the intrinsic viscosity have been investigated. The structure of the PCLA copolymers is characterized by means of nuclear magnetic resonance（ NMR ）, Fourier transform infrared spectrum （ FTIR ）, differential scanning calorimetry （ DSC ） and X- ray diffraction （ XRD ） methods. It is shown that the synthesis condition and the composition of copolymers obrious influence on the structure of PCLA copolymers. Hydrolytic degradation of the copolymers in a PBS solution of pH 7.4 at 37.0℃ shows that the copolymers of different composhions degrade at different rates.展开更多
Ti-incorporated mesoporous silica materials with pore diameters of 3-4 nm have been prepared via the co-hydrolysis and co-condensation reactions, that is the sol-gel reactions, of titanium (IV) tetrabutoxide and tetra...Ti-incorporated mesoporous silica materials with pore diameters of 3-4 nm have been prepared via the co-hydrolysis and co-condensation reactions, that is the sol-gel reactions, of titanium (IV) tetrabutoxide and tetraethylorthosilicate in the presence of tartaric acid as template, followed by extraction with ethanol to remove the templatemolecules. The materials were characterized in detail by Fourier transform infrared spectroscopy, nitrogen adsorption-desorption test, powder X-ray diffraction, transmission electron microscopy and X-ray energy dispersive spectroscopy. Theresults indicate that the Ti-containing silica materials have large specific surface areas (ca. 1200 m^2 g^(-1)) and pore volumes(ca. 0.900 cm^3 g^(-1)). The mesoporosity arises from disordered interconnecting channels or pores. The Ti-incorporated silicasexhibit catalytic activity for the ring-opening polymerization of ε-caprolactone, otherwise, the pure mesoporous silicamaterial shows no catalytic activity under the identical conditions.展开更多
Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C_2H_4C_5H_3CH_3)_2YCl (Cat-YCl) and Me_2Si[(CH_3)_3SiC_5H_3]_2NdCl(Cat-NdCl) has been carried out for the first time. It has been found...Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C_2H_4C_5H_3CH_3)_2YCl (Cat-YCl) and Me_2Si[(CH_3)_3SiC_5H_3]_2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization tem-perature is found to be the most important factor affecting the polymerization. The bulkpolymerization gives higher molecular weight PCL and higher conversion than that in solu-tion polymerization. NaBPh_4 was found to promote the polymerization of ε-caprolactone,and thus to increase both the polymerization conversion and MW of poly (ε- caprolactone ).展开更多
A new method to synthesize a degradable terminal amino group-containing copolymer,poly(ethylene glycol)-b- poly(ε-caprolactone)(MPEG-PCL-NH_2),was developed in the following three steps:(1)the ring-opening polymeriza...A new method to synthesize a degradable terminal amino group-containing copolymer,poly(ethylene glycol)-b- poly(ε-caprolactone)(MPEG-PCL-NH_2),was developed in the following three steps:(1)the ring-opening polymerization (ROP)ofε-caprolactone from the Schiff base prepared from benzatdehyde and ethanolamine(Ph-CH=NCH_2CH_2OH)used as an initiator to obtain heterobifunctional poly(ε-caprolactone)with one terminal Schiff base group and one hydroxyl group (HO-PCL-CH_2CH_2N=CH-Ph);(2)the coupling reaction of two ...展开更多
Transesterification of poly（ethylene terephthalate） （PET） with poly（ε-caprolactone） （PCL） was investigated bymeans of NMR spectroscopy, extraction experiments, differential scanning calorimetry （DSC） and ph...Transesterification of poly（ethylene terephthalate） （PET） with poly（ε-caprolactone） （PCL） was investigated bymeans of NMR spectroscopy, extraction experiments, differential scanning calorimetry （DSC） and phase contrast microscopy（PCM）. The;H-NMR results show that transesterification takes place in the melt blends and leads to the formation of thePET-PCL copolyester with a chemical structure similar to ethylene terephthalate-ε-caprolactonc copolycster （TCL）synthesized directly from monomers. However, even in the blend that has been transesterified for 8 h, the random PET-PCLcopolyester, PET-PCL copolyester with long PET or long PCL segments and the unreacted PET and PCL homopolymersmay coexist. Due to the low mobility of PET and PCL chains and the high viscosity of the two macromolecules, thetransesterification proceeds with difficulty. Furthermore, PET is incompatible with PCL, the transesterification can onlyoccur at the interface or in the interfacial region between two phases, and finally the reaction can only reach a localequilibrium. These results indicate that in fact the transesterification in the melt blend between two incompatiblehomopolymers could not lead to the formation of completely random or typical block copolyesters.展开更多
Copolymerizations of L-lactide （L-LA） and ε-caprolactone （ε-CL） were conducted in bulk using magnesium octoate as a catalyst. The reactivity ratios of L-LA and ε-CL were determined to be rL=23 and rc=0.22, resp...Copolymerizations of L-lactide （L-LA） and ε-caprolactone （ε-CL） were conducted in bulk using magnesium octoate as a catalyst. The reactivity ratios of L-LA and ε-CL were determined to be rL=23 and rc=0.22, respectively. The sequence analyses of the copolymers were performed on ^13C NMR. An increase in the reaction temperature enhances the role of transesterification and the extent of randomness.展开更多
A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ~ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiato...A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ~ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiator and stannous octanoate as a catalyst at 110 ℃ for 48 h. The molecular length of the PCL pre-polymer(BB) could be adjusted by controlling the molar ratio of the ethylene glycol initiator to ε-caprolactone monomer. The structure and the composition of the block copolymer were determined by the weight ratio of the monomer glycolide(A) to PCL pre-polymer(BB). The block copolymers were characterized by ~ 1H NMR, GPC, DSC and X-ray. The results confirm the successful synthesis of an ABBA block copolymer.展开更多
As an alternative biodegradable aliphatic polyester,poly(w-pentadecalactone-co-ε-caprolactone)copolymer was synthesized via enzymatic ring-opening polymerization.A new biocatalyst,Candida antarctica lipase B,immobili...As an alternative biodegradable aliphatic polyester,poly(w-pentadecalactone-co-ε-caprolactone)copolymer was synthesized via enzymatic ring-opening polymerization.A new biocatalyst,Candida antarctica lipase B,immobilized onto rice husk ash was used for catalysis.Reactions were carried out at various temperatures and periods for varied copolymer compositions in order to obtain the highest molecular weight copolymer.The best reaction parameters were found to be 80℃ and 6 hours and molecular weights increased proportionally with the amount of w-pentadecalactone(w-PDL).The molecular structure of copolymer with 75%weight ratio of w-PDL(Mn=19720 g/mol)was characterized by proton and carbon nuclear magnetic resonance spectroscopies(^1H-NMR and ^13C-NMR).Thermal properties of the same copolymer and homopolymers were investigated by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).Improved thermal features were shown by addition of w-PDL to the structure and compared with poly(ε-caprolactone)(PCL).Consequently,poly(w-pentadecalactone-co-ε-caprolactone)copolymers were found to be good alternatives to widely used polyester,PCL,with their rapid polymerization tendency,higher molecular weights,and improved thermal features.展开更多
基金This work was supported by the National Natural Science Foundation of China (No. 20404007).
文摘Both four-ann star-shaped poly（ε-caprolactone） （4sPCL） and two-ann linear PCL （2LPCL） were synthesized and their inclusion complexation with α-cyclodextrin （α-CD） were studied. The inclusion complexes （ICs） formed between the PCL polymers and α-CD were characterized by ^1H-NMR, DSC, TGA, WAXD, and FT-1R, respectively. Both branch ann number and molecular weight of the PCL polymers have apparent effect on the stoichiometry （CL：CD, mol：mol） of these ICs. All these analytical results indicate that the branch arms of the PCL polymers are incorporated into the hydrophobic α-CD cavities and their original crystalline properties are completely suppressed. Moreover, the inclusion complexation between two-ann linear or four-ann star-shaped PCL polymers and α-CD not only enhances the thermal stability of the guest PCL polymers but also improves that of α-CD.
文摘In the absence of catalyst,70%hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid(PSA).Then PSA was applied to synthesis ofε-caprolactone(ε-CL)by oxidation of cyclohexanone in the heterogeneous system.In order to achieve material recycle,solid precipitated in the process of synthesizingε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride,which was characterized by IR(infrared spectra)and1HNMR(1H nuclear magnetic resonance).Effects of molar ratio of PSA to cyclohexanone,acetic acid dosage,reaction temperature,reaction time on conversion of cyclohexanone,yield and selectivity ofε-CL were investigated respectively.The results indicated that conversion of cyclohexanone,yield and selectivity ofε-CL were upto 98.1%,97.5%and 99.4%respectively under the optimal conditions.In addition,in the process of synthesizing succinic anhydride,the optimal yield of succinic anhydride reached 67.4%.
基金supported by the National Key R&D Program of China (2016YFB0100500)Special fund of key technology research and development projects (20180201097GX) (20180201099GX) (20180201096GX) (20190302130GX)+1 种基金Jilin province science and technology department. The R&D Program of power batteries with low temperature and high energy, Science and Technology Bureau of Changchun (19SS013)Key Subject Construction of Physical Chemistry of Northeast Normal University。
文摘Inspired by the concept of "polymer-in-ceramic",a composite poly(ε-caprolactone)(PCL)/ceramic containing LiTFSI is prepared and investigated as a solid electrolyte for all-solid-state batteries.The composite with the optimum concentration of 45 wt% LiTFSI and 75 wt% Li1.5Al0.5Ge1.5(PO4)3(LAGP,NASICON-type structure) exhibits a high ionic conductivity(σi=0.17 mS cm-1) at 30℃,a transference number of 0.30,and is stable up to 5.0 V.The composite electrolyte is a flexible and self-standing membrane.Solid-state LiFePO4//Li batteries with this composite electrolyte demonstrate excellent cycling stability with high discharge capacity of 157 mA h g-1,high capacity retention of 96% and coulombic efficiency of 98.5% after 130 cycles at 30℃ and 0.1 C rate.These electrochemical properties are better than other PCL-based allsolid-lithium batteries,and validate the concept of "polymer-in-ceramic" by avoiding the drawback of lower conductivity in prior "polymer-in-ceramic" electrolyte at high concentration of the ceramic.
基金This work was financially supported by the Key Program of National Natural Science Foundation of China(No.G 20434020)the Special Funds for Major Basic Research Projects(No.G 2005 CB623802)the Committee of Science and Technology of Zhejiang Province.
文摘Ring-opening polymerization of ε-caprolactone has been carried out by using rare earth Schiff base complexes： lanthanide tris（N-phenyl-3,5-di-t-butylsalicylaldiminato）s [Ln（OPBS）3] as single component catalyst for the first time. The influences of different rare earth elements, monomer and catalyst concentration as well as reaction time on the polymerization were investigated. Mechanism studies showed that monomer inserts into the active site with the acyl-oxygen bond scission rather than the break of alkyl-oxygen bond.
基金National Natural Science Foundations of China(No.30970714,No.51103092)Natural Science Foundation of Jiangsu Province,China(No.BK2012634)+1 种基金College Natural Science Research Project of Jiangsu Province,China(No.12KJA430003)Priority Academic Program Development of Jiangsu Higher Education Institutions,China
文摘The mechanical properties and water solubility of electrospinning SF films limit their use as biomaterials. In order to develop a tissue engineering biomaterial with both satisfying biological properties and sufficient biomechanical properties,blended films composed of silk fibroin( SF) and poly( ε-caprolactone)( PCL) were fabricated by electrospinning in this study. Scanning electron microscope( SEM), X-ray diffraction( XRD),thermal analysis,Fourier transform-infrared( FT-IR),Raman spectra,mechanical testing,and water solubility were used to characterize the morphological, structural and mechanical properties of the blended electrospinning films. Results showed that the diameter of the blended fiber was distributed between 600 and1000 nm,and the fiber diameter increased as the PCL content increased. There is no obvious phase separation due to the similarity and intermiscibility,as well as the interactions( mainly hydrogen bonds), between the two polymers. Meanwhile, the secondary structures of SF changed from random coils and Silk I to Silk II because of the interactions between SF and PCL. For this reason,the tensile strength and elongation at break of the electrospinning films improved significantly,and the water solubility decreased. In conclusion,the blended electrospinning films fabricated in this study showed satisfying mechanical properties and water insolubilities,and they may be promising biomaterials for applications in tissue engineering for blood vessels,nerve conduits,tendons,ligaments and other tissues.
基金supported by grants from the Taichung Veterans General Hospital and Central Taiwan University of Science and Technology,No.TCVGH-CTUST1047701(to CCS and BSL)Taichung Veterans General Hospital,No.TCVGH-1034907C(to CCS),Taiwan,China
文摘Recent studies have shown the potential of artificially synthesized conduits in the repair of peripheral nerve injury. Natural biopolymers have received much attention because of their biocompatibility. To investigate the effects of novel electrospun absorbable poly(ε-caprolactone)/type Ⅰ collagen nanofiber conduits(biopolymer nanofiber conduits) on the repair of peripheral nerve injury, we bridged 10-mm-long sciatic nerve defects with electrospun absorbable biopolymer nanofiber conduits, poly(ε-caprolactone) or silicone conduits in Sprague-Dawley rats. Rat neurologica1 function was weekly evaluated using sciatic function index within8 weeks after repair. Eight weeks after repair, sciatic nerve myelin sheaths and axon morphology were observed by osmium tetroxide staining, hematoxylin-eosin staining, and transmission electron microscopy.S-100(Schwann cell marker) and CD4(inflammatory marker) immunoreactivities in sciatic nerve were detected by immunohistochemistry. In rats subjected to repair with electrospun absorbable biopolymer nanofiber conduits, no serious inflammatory reactions were observed in rat hind limbs, the morphology of myelin sheaths in the injured sciatic nerve was close to normal. CD4 immunoreactivity was obviously weaker in rats subjected to repair with electrospun absorbable biopolymer nanofiber conduits than in those subjected to repair with poly(ε-caprolactone) or silicone. Rats subjected to repair with electrospun absorbable biopolymer nanofiber conduits tended to have greater sciatic nerve function recovery than those receiving poly(ε-caprolactone) or silicone repair. These results suggest that electrospun absorbable poly(ε-caprolactone)/type Ⅰ collagen nanofiber conduits have the potential of repairing sciatic nerve defects and exhibit good biocompatibility. All experimental procedures were approved by Institutional Animal Care and Use Committee of Taichung Veteran General Hospital, Taiwan, China(La-1031218) on October 2, 2014.
基金The authors acknowledge the financial supports from National Nature Science Foundation（Nos. 20674071, 20774078 and 20434020） ；the Special Funds for Major State Basic Research Projects （No.2005CB623802）.
文摘Tetrahydrosalen ligand was employed in the synthesis of gadolinium complex. The ligand was deprotoned by LiBu, and the afforded lithium salt was reacted with anhydrous GdCl3 to produce the gadolinium complex through salt metathesis. This complex was successfully used to initiate the ring-opening polymerization of ε-caprolactone. The initiation conditions in different temperature, monomer-to-initiator ratio and time were investigated. Under the condition： [ε-caprolactone]：[catalyst] = 600, 56 ℃, toluene： 2 ml, poly（ε-caprolactone） （PCL） with Mw = 11,2782 and PDI = 1.96 was achieved.
文摘In this study a low molecular weight triblock copolymer derived fromε-caprolactone and tetrahydrofuran was used as a non-reactive compatibilizer of immiscible PLA/PCL blends.Ternary blends with 0,1.5 wt%,3 wt%and 5 wt% copolymer and about 75 wt%PLA were prepared by single screw extrusion and characterized by scanning electron microscopy(SEM),differential scanning calorimetry(DSC),dynamic mechanical analysis(DMA),tensile and Izod impact testing.SEM micrographs showed that the size of the dispersed PCL domains was practically constant regardless of copolymer concentration.This result can be explained by the low shear rate employed during processing step and a decrease of PCL viscosity by presence of the triblock copolymer.However,when the copolymer concentration increased,strain at break of PLA/PCL blends also increased.PLA/PCL blend with 0 wt% copolymer presented 2%strain at break,whereas PLA/PCL blend with 5 wt%copolymer exhibited 90%.
文摘Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gelpermeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found thatthe equilibrium melting points (T_m^0) of PCL samples depend on their molecular weights. Wide angle X-ray diffractionmeasurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were moreperfect than those of the low molecular weigh ones. These results demonstrate that the concentration of the end groups ofPCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (ΔH_u) wasdetermined to be 11.3 kJ/mol for PCL.
基金the National Natural Science Foundation of China(No.20774078)the Key Program of the National Natural Science Foundation of China(No.20434020)the Special Funds for Major Basic Research Projects(No.G 2005CB623802)
文摘An aromatic heterocyclic Schiff base neodymium complex bearing thiazole was synthesized and its activity in the ring-opening polymerization ofε-caprolactone(CL)was examined.The conditions of the CL/Nd molar ratio,monomer concentration,polymerization time and temperature were investigated.Activities of ca.171 kg/Nd·h were obtained under the optimum condition(CL/Nd=1600(molar ratio),[CL]=2.26 mol L^(-1),1 h at 50℃),giving a poly(ε-caprolactone)(PCL)of number-average molecular weight M_n=5.4×10~4 and molecular...
基金National Natural Science Foundations of China(Nos.31771048,31570984,31271028)International Cooperation Fund of the Science and Technology Commission of Shanghai Municipality,China(No.15540723400)Biomedical Textile Materials Science and Technology(111 Project),China(No.B07024)
文摘The ideal small-diameter vascular grafts should mimic the nanostructure and mechanical properties of nature blood vessel. In this study, electrospun chitosan( CS)/poly( L-lactic-co-ε-caprolactone)( PLCL) nanofibers were developed for potential small-diameter blood vessel applications. CS is a positively charged polymer which is beneficial for cell attachment and growth,while PLCL provides favorable mechanical support due to its excellent elasticity. Typical nanofibrous structure was observed in both CS/PLCL and pure PLCL scaffolds. The optimal mechanical property could be achieved when the weight ratio of CS/PLCL was 1 ∶ 2.Compared with pure PLCL scaffolds, the CS/PLCL scaffolds showed higher hydrophilicity and markedly promoted the attachment,spreading and proliferation of human umbilical vein endothelial cells( HUVECs). Hence,CS/PLCL scaffolds can be used as potential vascular grafts.
文摘Block copolyesters of L-lactide and ε-caprolactone were synthesized by melt copolymerization of ε-caprolactone and L-lactide.The degradation performance of copolyesters was investigated by quartz crystal microbalance with dissipation(QCM-D).Diisocyanate terminated copolyesters could obtain via the reaction of copolyesters and diisocyanate.Diisocyanate terminated copolyesters could react with polyol resin to prepare degradable polyurethane which can be used in antifouling coatings.In this paper,we also discussed the degradation products release action and antifouling performance of the copolyesters film.
文摘A series of random and block poly（ L-lactide-co-e-caprolactone ） （ PCLA ） copolymers whh different composition are prepared using stannous octaoate as catalyst.The effects of the amount of initiator on the intrinsic viscosity have been investigated. The structure of the PCLA copolymers is characterized by means of nuclear magnetic resonance（ NMR ）, Fourier transform infrared spectrum （ FTIR ）, differential scanning calorimetry （ DSC ） and X- ray diffraction （ XRD ） methods. It is shown that the synthesis condition and the composition of copolymers obrious influence on the structure of PCLA copolymers. Hydrolytic degradation of the copolymers in a PBS solution of pH 7.4 at 37.0℃ shows that the copolymers of different composhions degrade at different rates.
基金This work was supported by the National Natural Science Foundation of China (No. 29874002), and the Outstanding Young Scientist Award from the National Natural Science Foundation of China (No. 29825504).
文摘Ti-incorporated mesoporous silica materials with pore diameters of 3-4 nm have been prepared via the co-hydrolysis and co-condensation reactions, that is the sol-gel reactions, of titanium (IV) tetrabutoxide and tetraethylorthosilicate in the presence of tartaric acid as template, followed by extraction with ethanol to remove the templatemolecules. The materials were characterized in detail by Fourier transform infrared spectroscopy, nitrogen adsorption-desorption test, powder X-ray diffraction, transmission electron microscopy and X-ray energy dispersive spectroscopy. Theresults indicate that the Ti-containing silica materials have large specific surface areas (ca. 1200 m^2 g^(-1)) and pore volumes(ca. 0.900 cm^3 g^(-1)). The mesoporosity arises from disordered interconnecting channels or pores. The Ti-incorporated silicasexhibit catalytic activity for the ring-opening polymerization of ε-caprolactone, otherwise, the pure mesoporous silicamaterial shows no catalytic activity under the identical conditions.
文摘Ring-opening polymerization of ε-caprolactone (CL) catalyzed bylanthanocenes, O(C_2H_4C_5H_3CH_3)_2YCl (Cat-YCl) and Me_2Si[(CH_3)_3SiC_5H_3]_2NdCl(Cat-NdCl) has been carried out for the first time. It has been found that both yttroceneand neodymocene are very efficient to catalyze the polymerization of CL, giving high molec-ular weight poly (ε-caprolactone) (PCL ). The effects of [cat] / [ε- CL] molar ratio, polymeriza-tion temperature and time, as well as solvents were investigated and polymerization tem-perature is found to be the most important factor affecting the polymerization. The bulkpolymerization gives higher molecular weight PCL and higher conversion than that in solu-tion polymerization. NaBPh_4 was found to promote the polymerization of ε-caprolactone,and thus to increase both the polymerization conversion and MW of poly (ε- caprolactone ).
基金the National Natural Science Foundation of China(No.20574066)National Fund for Distinguished Young Scholar(No.50425309)
文摘A new method to synthesize a degradable terminal amino group-containing copolymer,poly(ethylene glycol)-b- poly(ε-caprolactone)(MPEG-PCL-NH_2),was developed in the following three steps:(1)the ring-opening polymerization (ROP)ofε-caprolactone from the Schiff base prepared from benzatdehyde and ethanolamine(Ph-CH=NCH_2CH_2OH)used as an initiator to obtain heterobifunctional poly(ε-caprolactone)with one terminal Schiff base group and one hydroxyl group (HO-PCL-CH_2CH_2N=CH-Ph);(2)the coupling reaction of two ...
基金This project was supported by the National Natural Science Foundation of China and the National Key Projects for Fundamental Research "Macromolecular Condensed State", The State Science and Technology Commission of China.
文摘Transesterification of poly（ethylene terephthalate） （PET） with poly（ε-caprolactone） （PCL） was investigated bymeans of NMR spectroscopy, extraction experiments, differential scanning calorimetry （DSC） and phase contrast microscopy（PCM）. The;H-NMR results show that transesterification takes place in the melt blends and leads to the formation of thePET-PCL copolyester with a chemical structure similar to ethylene terephthalate-ε-caprolactonc copolycster （TCL）synthesized directly from monomers. However, even in the blend that has been transesterified for 8 h, the random PET-PCLcopolyester, PET-PCL copolyester with long PET or long PCL segments and the unreacted PET and PCL homopolymersmay coexist. Due to the low mobility of PET and PCL chains and the high viscosity of the two macromolecules, thetransesterification proceeds with difficulty. Furthermore, PET is incompatible with PCL, the transesterification can onlyoccur at the interface or in the interfacial region between two phases, and finally the reaction can only reach a localequilibrium. These results indicate that in fact the transesterification in the melt blend between two incompatiblehomopolymers could not lead to the formation of completely random or typical block copolyesters.
文摘Copolymerizations of L-lactide （L-LA） and ε-caprolactone （ε-CL） were conducted in bulk using magnesium octoate as a catalyst. The reactivity ratios of L-LA and ε-CL were determined to be rL=23 and rc=0.22, respectively. The sequence analyses of the copolymers were performed on ^13C NMR. An increase in the reaction temperature enhances the role of transesterification and the extent of randomness.
文摘A biodegradable ABBA block copolymer was synthesized via the ring-opening co-polymerization of ~ε-caprolactone(CL, B) and glycolide(A) by means of step polymerization in the presence of ethylene glycol as an initiator and stannous octanoate as a catalyst at 110 ℃ for 48 h. The molecular length of the PCL pre-polymer(BB) could be adjusted by controlling the molar ratio of the ethylene glycol initiator to ε-caprolactone monomer. The structure and the composition of the block copolymer were determined by the weight ratio of the monomer glycolide(A) to PCL pre-polymer(BB). The block copolymers were characterized by ~ 1H NMR, GPC, DSC and X-ray. The results confirm the successful synthesis of an ABBA block copolymer.
文摘As an alternative biodegradable aliphatic polyester,poly(w-pentadecalactone-co-ε-caprolactone)copolymer was synthesized via enzymatic ring-opening polymerization.A new biocatalyst,Candida antarctica lipase B,immobilized onto rice husk ash was used for catalysis.Reactions were carried out at various temperatures and periods for varied copolymer compositions in order to obtain the highest molecular weight copolymer.The best reaction parameters were found to be 80℃ and 6 hours and molecular weights increased proportionally with the amount of w-pentadecalactone(w-PDL).The molecular structure of copolymer with 75%weight ratio of w-PDL(Mn=19720 g/mol)was characterized by proton and carbon nuclear magnetic resonance spectroscopies(^1H-NMR and ^13C-NMR).Thermal properties of the same copolymer and homopolymers were investigated by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).Improved thermal features were shown by addition of w-PDL to the structure and compared with poly(ε-caprolactone)(PCL).Consequently,poly(w-pentadecalactone-co-ε-caprolactone)copolymers were found to be good alternatives to widely used polyester,PCL,with their rapid polymerization tendency,higher molecular weights,and improved thermal features.
