In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was...In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was prepared.Hydrolytic degradation experiment revealed that the degradable polyurethane(PU)could be degraded in artificial seawater.It also showed that caprolactone-copolyurethane(CL-PU)copolymer with higher crystallinity degraded much slower in artificial seawater.However,the introduction of LLA resulted in an increase in the hydrophilicity and reduction in the crystallinity of degradable PU,as demonstrated by the contact angle analysis.The result of the scanning electron microscope showed that the surface of degradable PU renewed under static condition.Moreover,degradable PU was able to be used as a carrier,and it controlled the release rate of 4,5-dichloro-2-octyl-isothiazolone(DCOIT).The anti-diatom(Navicula incerta)test demonstrated that the(caprolactone-co-L-lactide)-co-polyurethane 4(CL/LAx-PU4)with DCOIT contents prevented the adhesion of diatom Navicula incerta(88.37%reduction)due to their self-polishing and the release of antifoulants.Therefore,the degradable PU consisted of CL,LLA,and DCOIT could be a durable resin with good antifouling activity for the application in the marine anti-biofouling field.展开更多
Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright fie...Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.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
The miscibility of poly(ethylene terephthalate (ET)- caprolactone (CL) (TCL)/poly(ethylene terephthalate) (PET) blends were examined by Differential Scanning Calorimeter (DSC). In these blends, a miscibility limit spe...The miscibility of poly(ethylene terephthalate (ET)- caprolactone (CL) (TCL)/poly(ethylene terephthalate) (PET) blends were examined by Differential Scanning Calorimeter (DSC). In these blends, a miscibility limit specified by ET content in the TCL was found to be about 70 (wt%). In the blends of TCL/TCL with different ET contents, a miscibility window defined by ET content was also found to range from 82 to 58 (wt%). Based on the experimental miscibility limits and the mean field binary interaction model, the interaction parameter between monomeric units of ET and CL was obtained.展开更多
Reaction of (MeC 5H 4) 3Ln with HOCH 2CH 2NMe 2 in tetrahydrofuran(THF) gives the new complexes [(MeC 5H 4) 2Ln(μ OCH 2CH 2NMe 2)] 2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ alkoxide ligand. The ...Reaction of (MeC 5H 4) 3Ln with HOCH 2CH 2NMe 2 in tetrahydrofuran(THF) gives the new complexes [(MeC 5H 4) 2Ln(μ OCH 2CH 2NMe 2)] 2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [(MeC 5H 4) 2Sm(μ OCH 2CH 2NMe 2)] 2 was structurally characterized by the X ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm-N bonds via intramolecular coordination of OCH 2CH 2NMe 2. The coordination number of the central metal Sm is nine. The title complexes show good catalytic activity for ring opening polymerization of ε caprolactone.展开更多
Mismatch in mechanical properties can induce intimal hyperplasia,which is one of the main reasons for the failure of small diameter artificial blood vessels. Electrospun small diameter tubes with tailored mechanical p...Mismatch in mechanical properties can induce intimal hyperplasia,which is one of the main reasons for the failure of small diameter artificial blood vessels. Electrospun small diameter tubes with tailored mechanical properties were fabricated through blending poly( L-lactide-co-ε-caprolactone)( PLCL) and silk fibroin( SF)with the mass ratios of 30 /70,50 /50,and 70 /30 in this study.Scanning electron microscopy( SEM) and mechanical testing were used to characterize morphological and mechanical properties of the tubes. Results showed that tensile strength of the tubes was higher than most of the native blood vessels,and elongations at break of them were improved greatly by blending PLCL. Compliances of the tubes were all higher than 1% /13. 33 kPa( 1% /100 mmHg).Particularly,tubes with blending mass ratio of 50 /50 showed similar compliance with human native femoral arteries,which provided a promising biomaterial that could be applied on small diameter vascular applications.展开更多
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
The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PC...The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.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
基金supported by the National Natural Science Foundation of China(21776249,21878267,21576236)。
文摘In this work,a degradable polyurethane composed of caprolactone(CL)and L-Lactide(LLA)as soft segments,and 4,40-methylenebis(cyclohexyl isocyanate)(H12 MDI)and polytetramethylene ether glycol(PTMEG)as hard segments,was prepared.Hydrolytic degradation experiment revealed that the degradable polyurethane(PU)could be degraded in artificial seawater.It also showed that caprolactone-copolyurethane(CL-PU)copolymer with higher crystallinity degraded much slower in artificial seawater.However,the introduction of LLA resulted in an increase in the hydrophilicity and reduction in the crystallinity of degradable PU,as demonstrated by the contact angle analysis.The result of the scanning electron microscope showed that the surface of degradable PU renewed under static condition.Moreover,degradable PU was able to be used as a carrier,and it controlled the release rate of 4,5-dichloro-2-octyl-isothiazolone(DCOIT).The anti-diatom(Navicula incerta)test demonstrated that the(caprolactone-co-L-lactide)-co-polyurethane 4(CL/LAx-PU4)with DCOIT contents prevented the adhesion of diatom Navicula incerta(88.37%reduction)due to their self-polishing and the release of antifoulants.Therefore,the degradable PU consisted of CL,LLA,and DCOIT could be a durable resin with good antifouling activity for the application in the marine anti-biofouling field.
文摘Electron microscope and electron diffraction have been used to study epitaxial crystallization of poly(ε-caprolactone)(PCL).on highly oriented film of isotactic polypropylene(iPP).The results obtained from bright field(BF)electron micrograph and electron diffraction indicate that the PCL can epitaxially grow on iPP substrate and form cross-hatched lamellar texture.The c axes of PCL are ±500 apart from the c axes of iPP. The contact planes of the two kinds of crystals are(010)of iPP and(100) of PCL,respectively.
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%.
文摘The miscibility of poly(ethylene terephthalate (ET)- caprolactone (CL) (TCL)/poly(ethylene terephthalate) (PET) blends were examined by Differential Scanning Calorimeter (DSC). In these blends, a miscibility limit specified by ET content in the TCL was found to be about 70 (wt%). In the blends of TCL/TCL with different ET contents, a miscibility window defined by ET content was also found to range from 82 to 58 (wt%). Based on the experimental miscibility limits and the mean field binary interaction model, the interaction parameter between monomeric units of ET and CL was obtained.
文摘Reaction of (MeC 5H 4) 3Ln with HOCH 2CH 2NMe 2 in tetrahydrofuran(THF) gives the new complexes [(MeC 5H 4) 2Ln(μ OCH 2CH 2NMe 2)] 2 (Ln=Sm, Y, Nd) with nitrogen functionalized μ alkoxide ligand. The complexes were characterized by elemental analysis and IR, and [(MeC 5H 4) 2Sm(μ OCH 2CH 2NMe 2)] 2 was structurally characterized by the X ray diffraction to be a dimer formed by two unsymmetric oxygen bridges. The complex has a tricyclic skeleton with the additional two Sm-N bonds via intramolecular coordination of OCH 2CH 2NMe 2. The coordination number of the central metal Sm is nine. The title complexes show good catalytic activity for ring opening polymerization of ε caprolactone.
基金National Natural Science Foundation of China(No.51103092)Natural Science Foundation of Jiangsu Province,China(No.BK2012634)
文摘Mismatch in mechanical properties can induce intimal hyperplasia,which is one of the main reasons for the failure of small diameter artificial blood vessels. Electrospun small diameter tubes with tailored mechanical properties were fabricated through blending poly( L-lactide-co-ε-caprolactone)( PLCL) and silk fibroin( SF)with the mass ratios of 30 /70,50 /50,and 70 /30 in this study.Scanning electron microscopy( SEM) and mechanical testing were used to characterize morphological and mechanical properties of the tubes. Results showed that tensile strength of the tubes was higher than most of the native blood vessels,and elongations at break of them were improved greatly by blending PLCL. Compliances of the tubes were all higher than 1% /13. 33 kPa( 1% /100 mmHg).Particularly,tubes with blending mass ratio of 50 /50 showed similar compliance with human native femoral arteries,which provided a promising biomaterial that could be applied on small diameter vascular applications.
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.
基金supported by the National Natural Science Foundation of China.(Grant No.20174033 and 20254001)the Special Found for Major State Basic Research Project(Grant No.G1999064801)the Committee of Science and Technology of Zhejiang Province.
文摘The ring-opening polymerization of e-caprolactone (CL) initiated by novel single lanthanide tris(4-tert-butylphenolate)s [Ln(OTBP)3] is reported. Single-component La(OTBP)3 can effectively prepare polycaprolactone (PCL) with over 90% yield and viscosity average molecular weight about 60 x 10 under quite mild conditions: molar ratio of CL to initiator is 1000, 60 C, 2 h in toluene. Mechanism study indicates that the monomer inserts into the growing chain via the break of acyl-oxygen bond of CL.
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.
