The ring-opening polymerization of D, L-lactide in the melt was systematically investigated by using stannous octoate as the initiator. The molecular weight of poly (D, L-lactide) was characterized with M,. Mn and Mw ...The ring-opening polymerization of D, L-lactide in the melt was systematically investigated by using stannous octoate as the initiator. The molecular weight of poly (D, L-lactide) was characterized with M,. Mn and Mw respectively. The results indicated that five variables, namely purity of monomer, initiator to monomer ratio, vacuum level, polymerization temperature and polymerization time had different influences on the molecular weight and molecular weight distribution of poly(D. L-lactide).展开更多
(D, L)-Lactide (LA) was first polymerized with one component of rare earth catalysts [Nd(naph)(3), Nd(oct)(3), Nd(O-iPr)(3), Nd(AcAc)(3), Y(AcAc)(3), Sm(AcAc)(3), Er(AcAc)(3))] respectively in solution and in melt sta...(D, L)-Lactide (LA) was first polymerized with one component of rare earth catalysts [Nd(naph)(3), Nd(oct)(3), Nd(O-iPr)(3), Nd(AcAc)(3), Y(AcAc)(3), Sm(AcAc)(3), Er(AcAc)(3))] respectively in solution and in melt state. The effects of [Cat]/[La] molar ratio, solvents, polymerization time, temperature, various rare earth Elements and ligands were investigated in detail. The results showed that both the conversion of polymerization and the molecular weight (MW) of poly (D, L-Lactide) (PLA) in melt polymerization are higher than that in solution polymerization, but the polymerization rate in melt was lower than in solution. The molecular weight distribution (MWD) of PLA is broader with increasing temperature. X-ray study indicated that PLA obtained by Nd(AcAc)(3) in melt polymerization is an amorphous polymer.展开更多
Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000...Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.展开更多
For monomer reactivity ratios study, the copolymerization of D,L-3-methylglycolide (MG) with glycolide (GA) or D,L-lactide (LA) was carried out in bulk to a certain low conversion in the presence of stannous octoate a...For monomer reactivity ratios study, the copolymerization of D,L-3-methylglycolide (MG) with glycolide (GA) or D,L-lactide (LA) was carried out in bulk to a certain low conversion in the presence of stannous octoate at 140 degrees C. The copolymer compositions were determined by H-1 NMR spectroscopy. The monomer reactivity ratios were evaluated by Fineman-Ross method, Kelen-Tudos method and linear least-squares method. The monomer reactivity ratios of D,L-3-methylglycolide and glycolide or D,L-lactide are r(mg)= 0.73, r(ga)= 1.47; r(mg)= 1.71, r(la)= 0.92, respectively.展开更多
Poly（d,l-lactide-co-p-dioxanone） （P（LA-co-PDO）） copolymers with different chain microstructures were synthesized by onestep or two-step bulk ring-opening polymerizations of d,l-lactide （LA） and p-dioxanone （...Poly（d,l-lactide-co-p-dioxanone） （P（LA-co-PDO）） copolymers with different chain microstructures were synthesized by onestep or two-step bulk ring-opening polymerizations of d,l-lactide （LA） and p-dioxanone （PDO） monomers using stannous octoate [Sn（Oct）2]/n-dodecanol as the initiating system. The average sequence lengths of the lactidyl （LLA） and dioxanyl （LpDo） units were calculated from the ^1H NMR spectra. It was found that both LLA and Lpoo values from the two-step syntheses were significantly longer than those from the corresponding one-step syntheses, indicating more blocky structure achieved for the twostep copolymers. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline, while the one-step copolymers were completely amorphous. In conclusion, the crystallinity of P（LA-co-PDO） copolymers could be adjusted conveniently to meet specific applications by changing the microstructure of the copolymers via different polymerization routes.展开更多
Single component rare earth phenolates substituted by various alkyl groups have been prepared and the correlation between the aryloxides＇ structure and catalytic activity in the ring-opening polymerization of D,L-lac...Single component rare earth phenolates substituted by various alkyl groups have been prepared and the correlation between the aryloxides＇ structure and catalytic activity in the ring-opening polymerization of D,L-lactide has also been investigated.The catalytic activity of all rare earth aryloxides,characteristics of the ring-opening polymerization as well as polymerization kinetics and mechanism were investigated.The results showed that both phenolates＇ catalytic activities and polymerization characteristics changed regularly,keeping in good concordance with variations in substitutents＇ number on phenol and structure of aryloxide ligands.The stronger ability of electron-donation of alkyl groups,the higher catalytic activity.Moreover,the more numbers of substituted alkyl on phenyl ring,the higher catalytic activity.The analyses of polymer ends revealed that the polymerization proceeded via a coordination-acyl-oxygen bond cleavage-insertion mechanism.展开更多
Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critica...Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.展开更多
The starch/D,L-lactide graft copolymers were synthesized by reacting D,L-lactide with corn starch in N,N-dimethylacetamide (DMAM) in the presence of triethylamine (NEt3) and anhydrous lithium chloride. The effect of r...The starch/D,L-lactide graft copolymers were synthesized by reacting D,L-lactide with corn starch in N,N-dimethylacetamide (DMAM) in the presence of triethylamine (NEt3) and anhydrous lithium chloride. The effect of reaction time and the molar ratio of D,L-lactide to glucose structural unit of starch on monomer conversion(C%), graft (G%) and graft efficiency (GE%) were studied. The C%, G% and GE% could approach 37.3%,179.7% and 68.0%, respectively when the molar ratio of D,L-lactide to glucose structural unit of starch is 10:1 and the graft copolymerization was carried out at 80-85℃ for 4 hours under nitrogen atmosphere. The Fourier transforms infra-red (FTIR) spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) spectroscopy were used in order to characterize the graft copolymers. FTIR spectra show that absorption band at 1740 cm-1 confirmed the formation of ester bond, indicating the starch /D,L-lactide graft copolymers were produced, the DSC characteristic results show the melting temperature of the graft copolymer were elevated slightly as the molar ratio of D,L-lactide to glucose structural units of starch increased and the X-ray diffraction spectra show the synthesized graft copolymers were amorphous. The degradability of graft copolymer was tested with the aid of acid, alkali and microbe such as bacillus subtilis and staphylococcus aureus. The results of water resistance show the graft copolymer produced can be used as a component of impermeable coating for cardboard.展开更多
Monopiles are the most common foundation form of offshore wind turbines,which bear the vertical load,lateral load and bending moment.It remains uncertain whether the applied vertical load increases the lateral deflect...Monopiles are the most common foundation form of offshore wind turbines,which bear the vertical load,lateral load and bending moment.It remains uncertain whether the applied vertical load increases the lateral deflection of the pile.This paper investigated the influence of vertical load on the behaviour of monopiles installed in the sand under combined load using three-dimensional numerical methods.The commercial software PLAXIS was used for simulations in this paper.Monopiles were modelled as a structure incorporating linear elastic material behaviour and soil was modelled using the Hardening-Soil(HS)constitutive model.The monopiles under vertical load,lateral load and combined vertical and lateral loads were respectively studied taking into account the sequence of load application and pile slenderness ratio(L/D;L and D are the length and diameter of the pile).Results suggest that the sequence of load application plays a major role in how vertical load affects the deflection behaviour of the pile.Specifically,when L/D ratios obtained by lengthening the pile while keeping its diameter constant are 3,5 and 8,the relationships between lateral load and the deflection behaviour of the pile under the effect of vertical load demonstrate a similar trend.Furthermore,the cause of increased lateral capacity of the pile under the action of applied vertical load in the common practical application case and in the VPL case was analyzed by studying the variation law of soil stress along the pile embedment.Results confirm that the confining effect of vertical load increases means effective stress of the soil around the pile,thus increasing soil stiffness and pile capacity.展开更多
基金Funded by the Key Project of the Ministry of Science and Technology (No. 96 - 920 - 20 - 21)
文摘The ring-opening polymerization of D, L-lactide in the melt was systematically investigated by using stannous octoate as the initiator. The molecular weight of poly (D, L-lactide) was characterized with M,. Mn and Mw respectively. The results indicated that five variables, namely purity of monomer, initiator to monomer ratio, vacuum level, polymerization temperature and polymerization time had different influences on the molecular weight and molecular weight distribution of poly(D. L-lactide).
基金This work was supported by the National Natural Science Foundation of China and the Laboratory of Rare-earth Chemistry and Physics,Changchun Institute of Applied Chemistry,Academia Sinica
文摘(D, L)-Lactide (LA) was first polymerized with one component of rare earth catalysts [Nd(naph)(3), Nd(oct)(3), Nd(O-iPr)(3), Nd(AcAc)(3), Y(AcAc)(3), Sm(AcAc)(3), Er(AcAc)(3))] respectively in solution and in melt state. The effects of [Cat]/[La] molar ratio, solvents, polymerization time, temperature, various rare earth Elements and ligands were investigated in detail. The results showed that both the conversion of polymerization and the molecular weight (MW) of poly (D, L-Lactide) (PLA) in melt polymerization are higher than that in solution polymerization, but the polymerization rate in melt was lower than in solution. The molecular weight distribution (MWD) of PLA is broader with increasing temperature. X-ray study indicated that PLA obtained by Nd(AcAc)(3) in melt polymerization is an amorphous polymer.
文摘Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening polymerization of D, L-lactide with stannous octanoate (SnOct(2)) as catalyst. Its weight-average molar mass (M-w) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.
基金This work was supported by the Key Project of the National Natural Science Foundation of China!(59833 140).
文摘For monomer reactivity ratios study, the copolymerization of D,L-3-methylglycolide (MG) with glycolide (GA) or D,L-lactide (LA) was carried out in bulk to a certain low conversion in the presence of stannous octoate at 140 degrees C. The copolymer compositions were determined by H-1 NMR spectroscopy. The monomer reactivity ratios were evaluated by Fineman-Ross method, Kelen-Tudos method and linear least-squares method. The monomer reactivity ratios of D,L-3-methylglycolide and glycolide or D,L-lactide are r(mg)= 0.73, r(ga)= 1.47; r(mg)= 1.71, r(la)= 0.92, respectively.
基金supported by the National Natural Sciences Fund of China(No.50603025)the Opening Project of State Key Laboratory of Polymer Materials Engineering(Sichuan University).
文摘Poly（d,l-lactide-co-p-dioxanone） （P（LA-co-PDO）） copolymers with different chain microstructures were synthesized by onestep or two-step bulk ring-opening polymerizations of d,l-lactide （LA） and p-dioxanone （PDO） monomers using stannous octoate [Sn（Oct）2]/n-dodecanol as the initiating system. The average sequence lengths of the lactidyl （LLA） and dioxanyl （LpDo） units were calculated from the ^1H NMR spectra. It was found that both LLA and Lpoo values from the two-step syntheses were significantly longer than those from the corresponding one-step syntheses, indicating more blocky structure achieved for the twostep copolymers. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline, while the one-step copolymers were completely amorphous. In conclusion, the crystallinity of P（LA-co-PDO） copolymers could be adjusted conveniently to meet specific applications by changing the microstructure of the copolymers via different polymerization routes.
基金Funded by the Natural Science Foundation of Shanxi Province (No.2006011069)the Opening Foundation of Key Laboratory of Shanxi Province (No.2009011059-7)
文摘Single component rare earth phenolates substituted by various alkyl groups have been prepared and the correlation between the aryloxides＇ structure and catalytic activity in the ring-opening polymerization of D,L-lactide has also been investigated.The catalytic activity of all rare earth aryloxides,characteristics of the ring-opening polymerization as well as polymerization kinetics and mechanism were investigated.The results showed that both phenolates＇ catalytic activities and polymerization characteristics changed regularly,keeping in good concordance with variations in substitutents＇ number on phenol and structure of aryloxide ligands.The stronger ability of electron-donation of alkyl groups,the higher catalytic activity.Moreover,the more numbers of substituted alkyl on phenyl ring,the higher catalytic activity.The analyses of polymer ends revealed that the polymerization proceeded via a coordination-acyl-oxygen bond cleavage-insertion mechanism.
文摘Methoxy poly(ethylene glycol)-poly(D,L-lactide) block copolymers (PEG-PLA) were prepared through ring-opening polymerization.The oil in water suspension method was used to prepare block copolymer micelles. The critical micelle concentration (CMC) by fluorescence spectroscopy was 0.0056 mg·ml -1 . The physical state of the inner core region of micelles was characterized with 1HNMR. The size of indomethacin (IMC) loaded micelles measured by dynamic light scattering (DLS) showed narrow monodisperse size distribution and the average diameters were less than 50 nm. In addition, the nanoparticles with relatively high drug loading content (DLC) were obtained.
文摘The starch/D,L-lactide graft copolymers were synthesized by reacting D,L-lactide with corn starch in N,N-dimethylacetamide (DMAM) in the presence of triethylamine (NEt3) and anhydrous lithium chloride. The effect of reaction time and the molar ratio of D,L-lactide to glucose structural unit of starch on monomer conversion(C%), graft (G%) and graft efficiency (GE%) were studied. The C%, G% and GE% could approach 37.3%,179.7% and 68.0%, respectively when the molar ratio of D,L-lactide to glucose structural unit of starch is 10:1 and the graft copolymerization was carried out at 80-85℃ for 4 hours under nitrogen atmosphere. The Fourier transforms infra-red (FTIR) spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) spectroscopy were used in order to characterize the graft copolymers. FTIR spectra show that absorption band at 1740 cm-1 confirmed the formation of ester bond, indicating the starch /D,L-lactide graft copolymers were produced, the DSC characteristic results show the melting temperature of the graft copolymer were elevated slightly as the molar ratio of D,L-lactide to glucose structural units of starch increased and the X-ray diffraction spectra show the synthesized graft copolymers were amorphous. The degradability of graft copolymer was tested with the aid of acid, alkali and microbe such as bacillus subtilis and staphylococcus aureus. The results of water resistance show the graft copolymer produced can be used as a component of impermeable coating for cardboard.
文摘Monopiles are the most common foundation form of offshore wind turbines,which bear the vertical load,lateral load and bending moment.It remains uncertain whether the applied vertical load increases the lateral deflection of the pile.This paper investigated the influence of vertical load on the behaviour of monopiles installed in the sand under combined load using three-dimensional numerical methods.The commercial software PLAXIS was used for simulations in this paper.Monopiles were modelled as a structure incorporating linear elastic material behaviour and soil was modelled using the Hardening-Soil(HS)constitutive model.The monopiles under vertical load,lateral load and combined vertical and lateral loads were respectively studied taking into account the sequence of load application and pile slenderness ratio(L/D;L and D are the length and diameter of the pile).Results suggest that the sequence of load application plays a major role in how vertical load affects the deflection behaviour of the pile.Specifically,when L/D ratios obtained by lengthening the pile while keeping its diameter constant are 3,5 and 8,the relationships between lateral load and the deflection behaviour of the pile under the effect of vertical load demonstrate a similar trend.Furthermore,the cause of increased lateral capacity of the pile under the action of applied vertical load in the common practical application case and in the VPL case was analyzed by studying the variation law of soil stress along the pile embedment.Results confirm that the confining effect of vertical load increases means effective stress of the soil around the pile,thus increasing soil stiffness and pile capacity.
