PREPARATION AND CHARACTERIZATION OF INCLUSION COMPLEXES OF TWO-ARM LINEAR AND FOUR-ARM STAR-SHAPED POLY(ε-CAPROLACTONE)S WITHα-CYCLODEXTRIN

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.

“Polymer-in-ceramic” based poly(ε-caprolactone)/ceramic composite electrolyte for all-solid-state batteries

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.

Synthesis and Characterization of Degraded Gelatin Grafted Poly(ε-caprolactone) Copolymers

Hydrophilic degraded gelatin was modified with hydrophobic poly(ε-caprolactone) (PCL) via a chemical grafting route.Firstly,PCL with one hydroxyl end group was prepared by the ring-opening polymerization of εcaprolactone (ε-CL) with tin (Ⅱ) 2-ethylhexanoate as catalyst and n-butyl alcohol as initiator.Secondly,the PCL reacted with isophorone diisocyanate (IPDI) to prepare PCL with isocyanate functional group (PCL-NCO).Hydroxylamine was used to degrade gelatin by the cleavage between asparagine and glycine residues of gelatin.PCL-NCO reacted with the hydroxyl/amino groups of degraded gelatin in a homogeneous system and yielded the PCL modified gelatin copolymers.The gelatin grafted PCL copolymers were measured by means of XRD,FTIR,DSC and 1 H NMR.The results confirmed the conjugation of PCL onto gelatin chains.The PCL modified gelatin can be used as biomaterials owing to their biocompatibility and biodegradation.

RING-OPENING POLYMERIZATION OFε-CAPROLACTONE USING LANTHANIDE TRIS(N-PHENYL-3,5-DI-T-BUTYLSALICYLALDIMINATO)S AS SINGLE COMPONENT CATALYST

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.

Novel electrospun poly(ε-caprolactone)/type Ⅰ collagen nanofiber conduits for repair of peripheral nerve injury

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 within 8 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.

Structure Changes of Silk Fibroin(SF) by Blending with Poly(ε-caprolactone)(PCL):Characterization of SF and PCL Blended Electrospinning Films

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.

Tetrahydrosalen backboned gadolinium complex as initiator for the ring-opening polymerization of ε-caprolactone

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.

HETEROCYCLIC SCHIFF BASE NEODYMIUM COMPLEX AS CATALYST FOR RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE

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...

Electrospun Chitosan( CS)/Poly( L-lactic-co-ε-caprolactone)( PLCL ) Nanofibers and Their Potential as Small-Diameter Vascular Scaffold

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.

Research in the Degradation and Antifouling Performance of Copolyesters of L-Lactide and ε-Caprolactonen

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.

Synthesis and Characterization of Poly(L-lactide-co-ε-caprolactone) Copolymers

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.

TARTARIC ACID TEMPLATED SYNTHESIS OF MESOPOROUS Ti-INCORPORATED SILICA AND ITS CATALYTIC ACTIVITY FOR THE RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE

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.

RING-OPENING POLYMERIZATION OF ε-CAPROLACTONE BY LANTHANOCENE CATALYSIS

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 ).

TRANSESTERIFICATION OF POLY(ETHYLENE TEREPHTHALATE) WITH POLY(ε-CAPROLACTONE)

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.

The copolymerization of L-lactide andε-caprolactone using magnesium octoate as a catalyst

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.

AN APPROACH TO SYNTHESIZE POLY(ETHYLENE GLYCOL)-b-POLY(ε-CAPROLACTONE) WITH TERMINAL AMINO GROUP via SCHIFF'S BASE AS AN INITIATOR

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 ...

Synthesis and Characterization of ABBA Block Copolymer of Glycolide and ε-Caprolactone

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.

Enzymatic Synthesis and Characterization of Biodegradable Poly(w-pentadecalactone-co-ε-caprolactone)Copolymers

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.

Lanthanum heterocyclic Schiff-base complex initiated ring-opening polymerization of ε-caprolactone

Lanthanum complex supported by the heterocyclic Schiff-base ligand of N-(2-pyridyl)-3,5-di-tert-butyl-salicylaldimine was prepared and employed for the ring-opening polymerization(ROP)ofε-caprolactone(ε-CL).The polymers obtained with this initiator showed a unimodal molecular weight distribution implied that only one active species was present.Mechanism study revealed that the polymerization proceeds via acyl-oxygen bond cleavage.

In situ generated,tetrahydrosalen stabilized yttrium borohydride complex:Efficient initiator for the ring-opening polymerization of ε-caprolactone

In this paper, we report the preparation of a new tertrahydrosalen-stabilized yttrium complex which was employed as an initiator-precursor for the polymerization of ε-caprolactone （ε-CL） in the presence of NaBH4 to give interesting hydroxytelechelic poly（ε-caprolactone） （PCL）. The effect of [monomer]/[initiator] （[CL]/[I]）, temperature and time on the polymerization was investigated. It was found that under the condition： [CL]/[I] = 1200, 55℃, toluene： 0.5 mL, ε-CL： 0.5 mL, PCL with Mw = 32,600 and PDI = 1.47 was obtained.