Currently, phosphate based glasses have been potential future biomaterial for medical application due to excellent cytocompatibility and fully bioresorbability. In this study, phosphate based glass system with composi...Currently, phosphate based glasses have been potential future biomaterial for medical application due to excellent cytocompatibility and fully bioresorbability. In this study, phosphate based glass system with composition of 48P2O5-12B2O3-(25-X)MgO-14CaO-1Na2O-(X)Fe2O3 (X = 6, 8, 10) and 45P2O5-(Y)B2O3-(32-Y)MgO-14CaO-1Na2O-8Fe2O3 (Y = 12, 15, 20), was prepared via a melting quenching process. The effect of replacing MgO with Fe2O3 and B2O3 on the structural, thermal, degradation properties of phosphate based glass was investigated. Fourier Transform Infrared (FTIR) spectroscopy and Raman spectroscopy analysis confirmed the polymerisation of phosphate based glass network with addition of Fe2O3, thus the processing window was observed to increase whilst the dissolution rate was reduced, attributed to the formation of Fe-O-P cross-link. As the effect on the glass structure stability was demonstrated by both B2O3 and MgO, the nonlinear variation of thermal stability and degradation behaviour was observed for glass system with substitution of MgO by B2O3. However, due to the lower dissolution rate of glass system when compared to the biocompatible phosphate based glass in preliminary study, the expected cytocompatibility could be confirmed in the downstream activities.展开更多
Novel, self-associating hybrid copolymers were synthesized via controlled ring-opening polymerization of N-carboxyanhydride of Z-L-lysine (Z-L-Lys-NCA), initiated by amino-functional macroinitiators. A poly(N-isopropy...Novel, self-associating hybrid copolymers were synthesized via controlled ring-opening polymerization of N-carboxyanhydride of Z-L-lysine (Z-L-Lys-NCA), initiated by amino-functional macroinitiators. A poly(N-isopropylacry-lamide) (PNIPAm)-based macroinitiator containing 10 mol% of polyoxyethylene grafts and a terminal primary amine group in the form of ammonium hydrochloride (PNIPAm-g-PEО) was synthesized and used to initiate the ammonium- mediated ring-opening polymerization of NCA described by Dimitrov and Schlaad [1]. Thus, hybrid copolymers ((PNIPAm-g-PEO)-b-PLys) with controlled molar-mass characteristics and functionality were obtained. The potential applications of PNIPAm-based copolymers in the systems for controlled drug release, immobilization of enzymes and protein purification have aroused great interest in the studies of their properties and behaviour. The thermal stability and thermodynamic properties of the copolymers obtained were studied. The differential thermal analysis of polyfunctional hybrid copolymers (PNIPAm-g-PEO)-b-PLys) showed that thermooxidative destruction occurs in two stages: primary, of the unstable fragments (grafted chains of PEO);and secondary, of the main polymer chains of poly(N-isopropylacry-lamide) and poly(L-lysine). The kinetics of thermal degradation was evaluated and the values of the activation energy of the degradation process, changes of Gibbs free energy, enthalpy and entropy for the formation of the activated complex were also calculated.展开更多
Many researchers have shown interest in the reinforcement of commodity thermoplastic with natural fibers. However, the drawback of natural fibers is their low thermal processing temperatures, that border around 200℃....Many researchers have shown interest in the reinforcement of commodity thermoplastic with natural fibers. However, the drawback of natural fibers is their low thermal processing temperatures, that border around 200℃. In this investigation, we tried to improve the thermal stability of natural fibers with the use of flexible epoxy surface coating that could facilitate processing with engineering thermoplastics. Jute fabric and Polyamide 6 (PA6) composites were prepared by compression molding. The thermal decomposition characteristics of the jute fabric were evaluated by using thermo gravimetric analysis (TGA). Mechanical analysis was conducted to evaluate tensile test and three point bending test of composite. It was found that thermal degradation resistance of jute fabric was improved by coating with flexible epoxy resin. Moreover, the flexural modulus improved with increasing curative concentration. The interfacial interaction between the epoxy and PA6 was clearly indicated by the photo micrographs of the polished cross sections of the coated and uncoated jute fabric/PA6 composites.展开更多
Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scann...Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scanning calorimetry and thermogravimetry analysis.The polystyrene-equivalent number-average(Mn)and weight-average molecular weight(Mw)of these polyesters ranged from 4900-11100 Da and 7900-20879 Da,respectively,with PDI values of 1.48-1.98.The melting point varied from 62.3-127.9℃,and the 50%mass-loss temperature ranged between 387-417℃.The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH.Weight losses of 14%-26%were obtained at pH 7.0,26%-38%at pH 6.0,and 32%-43%at pH 8.3 over a 20-week period.The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida.These results indicate that these polyesters have a combination of good thermal and degradability behaviors,which can be tailored through selection of the diol monomers used in the synthesis.展开更多
Aluminum hypophosphite （AP） was used to prepare flame-retarded thermoplastic polyurethane （FR-TPU） composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limitin...Aluminum hypophosphite （AP） was used to prepare flame-retarded thermoplastic polyurethane （FR-TPU） composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limiting oxygen index （LOI）, vertical burning test （UL-94）, thermogravimetric analysis （TGA）, cone calorimeter （CC） test, Fourier transform infrared （FTIR） spectroscopy, scanning electron microscopy （SEM） and tensile test. TPU containing 30 wt% of AP could reach a V-0 rating in the UL-94 test, and its LOI value was 30.2. TGA tests revealed that AP enhanced the formation of residual chars at high temperatures, and slightly affected the thermal stability of TPU at high temperatures. The combustion tests indicated that AP affected the burning behavior of TPU. The peak of heat release rate （PHRR）, total heat release （THR） and mass loss rate （MLR） greatly reduced due to the incorporation of AP. The tensile test results showed that both the tensile strength and the elongation at break slightly decreased with the addition of AP. The digital photos and SEM micrographs vitrified that AP facilitated the formation of more compact intumescent char layer. Based on these results mentioned above, the flame-retarding mechanism of AP was discussed. Both the self-charring during the decomposing process of AP and its facilitation to the charring of TPU led to the great improvement in the flame retardancy of TPU.展开更多
A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR,13C NMR,31P ...A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR,13C NMR,31P NMR,FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA),differential scanning calorimentry (DSC) and FTIR,while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss,and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions,it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37℃. And the sample hydrolytic degradation still remains at the stage of side groups' break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP),hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%,47% and 47% at 800℃,respectively,probably due to cross-linking between molecules.展开更多
Octyl(triphenylethynyl)silane monomer(OTPES)was synthesized with ethyl bromide,octyltrichlorosilane and phenylethylene by Grignard reaction.The molecular structure was confirmed by FTIR and NMR.The poly[octyl(tripheny...Octyl(triphenylethynyl)silane monomer(OTPES)was synthesized with ethyl bromide,octyltrichlorosilane and phenylethylene by Grignard reaction.The molecular structure was confirmed by FTIR and NMR.The poly[octyl(triphenylethynyl)]silane resin(POTPES)was prepared by thermal polymerization and the corresponding thermal degradation behavior wasstudied by thermogravimetric analysis(TG)combining with model and model-free fitted methods.The dielectric property of resin was also studied by vector network analyzer.The results show that the melt point of OTPES was 50℃ and the processing window was over 236℃.The resin degradation temperature of Td5 occurred over 433℃ and the char yield was over 60%at 800℃.Based on Kissinger,Flynn-Wall-Ozawa,Coats-Redfern,Achar,Vyazovkin-Wight and Tang methods,the reaction activity(E)was 155.51,152.97,150.82,146.02,148.38 and 148.77 kJ/mol,respectively.Dielectric properties analysis displayed that the real part(ε′)and the imaginary part(ε″)of the relative complex permittivity of POTPES was 2.5 and 0.05,respectively,and the dielectric loss tangent was between 0.03 and 0.25.The reflection loss of resin was more than?2.85 dB in all range of 1–5 mm thicknesses and 2–18 GHz frequency,which indicated that POTPES resin was a real wave-transparent resin matrix.展开更多
A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR...A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR and ^(1)H NMR spectroscopy,gel permeation chromatography(GPC)and differential scanning calorimetry(DSC)analysis.The polydispersity index(PDI=M_(w)/M_(n))of the polyesters ranged from 1.55 to 1.99,the weight-average molecular weight(M_(w))from 1.8×10^(4) to 3.2×10^(4) Da,the melting point from 63 to 123℃,and the highest decomposition temperature observed was 363℃.The influence of the structure of the polymer chain on hydrolytic degradability was investigated with tests performed at three different values of pH.The findings obtained provide useful insight for the molecular design and the synthesis of degradable polyesters.展开更多
文摘Currently, phosphate based glasses have been potential future biomaterial for medical application due to excellent cytocompatibility and fully bioresorbability. In this study, phosphate based glass system with composition of 48P2O5-12B2O3-(25-X)MgO-14CaO-1Na2O-(X)Fe2O3 (X = 6, 8, 10) and 45P2O5-(Y)B2O3-(32-Y)MgO-14CaO-1Na2O-8Fe2O3 (Y = 12, 15, 20), was prepared via a melting quenching process. The effect of replacing MgO with Fe2O3 and B2O3 on the structural, thermal, degradation properties of phosphate based glass was investigated. Fourier Transform Infrared (FTIR) spectroscopy and Raman spectroscopy analysis confirmed the polymerisation of phosphate based glass network with addition of Fe2O3, thus the processing window was observed to increase whilst the dissolution rate was reduced, attributed to the formation of Fe-O-P cross-link. As the effect on the glass structure stability was demonstrated by both B2O3 and MgO, the nonlinear variation of thermal stability and degradation behaviour was observed for glass system with substitution of MgO by B2O3. However, due to the lower dissolution rate of glass system when compared to the biocompatible phosphate based glass in preliminary study, the expected cytocompatibility could be confirmed in the downstream activities.
文摘Novel, self-associating hybrid copolymers were synthesized via controlled ring-opening polymerization of N-carboxyanhydride of Z-L-lysine (Z-L-Lys-NCA), initiated by amino-functional macroinitiators. A poly(N-isopropylacry-lamide) (PNIPAm)-based macroinitiator containing 10 mol% of polyoxyethylene grafts and a terminal primary amine group in the form of ammonium hydrochloride (PNIPAm-g-PEО) was synthesized and used to initiate the ammonium- mediated ring-opening polymerization of NCA described by Dimitrov and Schlaad [1]. Thus, hybrid copolymers ((PNIPAm-g-PEO)-b-PLys) with controlled molar-mass characteristics and functionality were obtained. The potential applications of PNIPAm-based copolymers in the systems for controlled drug release, immobilization of enzymes and protein purification have aroused great interest in the studies of their properties and behaviour. The thermal stability and thermodynamic properties of the copolymers obtained were studied. The differential thermal analysis of polyfunctional hybrid copolymers (PNIPAm-g-PEO)-b-PLys) showed that thermooxidative destruction occurs in two stages: primary, of the unstable fragments (grafted chains of PEO);and secondary, of the main polymer chains of poly(N-isopropylacry-lamide) and poly(L-lysine). The kinetics of thermal degradation was evaluated and the values of the activation energy of the degradation process, changes of Gibbs free energy, enthalpy and entropy for the formation of the activated complex were also calculated.
文摘Many researchers have shown interest in the reinforcement of commodity thermoplastic with natural fibers. However, the drawback of natural fibers is their low thermal processing temperatures, that border around 200℃. In this investigation, we tried to improve the thermal stability of natural fibers with the use of flexible epoxy surface coating that could facilitate processing with engineering thermoplastics. Jute fabric and Polyamide 6 (PA6) composites were prepared by compression molding. The thermal decomposition characteristics of the jute fabric were evaluated by using thermo gravimetric analysis (TGA). Mechanical analysis was conducted to evaluate tensile test and three point bending test of composite. It was found that thermal degradation resistance of jute fabric was improved by coating with flexible epoxy resin. Moreover, the flexural modulus improved with increasing curative concentration. The interfacial interaction between the epoxy and PA6 was clearly indicated by the photo micrographs of the polished cross sections of the coated and uncoated jute fabric/PA6 composites.
基金Funded by the Program (BG20190227001)of High-end Foreign Experts of the State Administration of Foreign Experts Affairs (SAFEA)the Coal Conversion and New Carbon Materials Hubei Key Laboratory at Wuhan University of Science and Technology (WKDM202005)。
文摘Six novel hydrolytically degradable polyesters were synthesized from thiodipropionic acid(TDPA)and five diols by melt polycondensation,and characterized by FT-IR,1H NMR,gel permeation chromatography,differential scanning calorimetry and thermogravimetry analysis.The polystyrene-equivalent number-average(Mn)and weight-average molecular weight(Mw)of these polyesters ranged from 4900-11100 Da and 7900-20879 Da,respectively,with PDI values of 1.48-1.98.The melting point varied from 62.3-127.9℃,and the 50%mass-loss temperature ranged between 387-417℃.The degradation of these polyesters was studied in terms of relative weight loss in distilled water at different pH.Weight losses of 14%-26%were obtained at pH 7.0,26%-38%at pH 6.0,and 32%-43%at pH 8.3 over a 20-week period.The ecotoxicity study suggested that safety of the synthesized polyesters for the eisenia foetida.These results indicate that these polyesters have a combination of good thermal and degradability behaviors,which can be tailored through selection of the diol monomers used in the synthesis.
基金financially supported by the National Natural Science Foundation of China(Nos.50933005 and 51121001)the Program for Changjiang Scholars and Innovative Research Teams in Universities of China(IRT 1026)
文摘Aluminum hypophosphite （AP） was used to prepare flame-retarded thermoplastic polyurethane （FR-TPU） composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limiting oxygen index （LOI）, vertical burning test （UL-94）, thermogravimetric analysis （TGA）, cone calorimeter （CC） test, Fourier transform infrared （FTIR） spectroscopy, scanning electron microscopy （SEM） and tensile test. TPU containing 30 wt% of AP could reach a V-0 rating in the UL-94 test, and its LOI value was 30.2. TGA tests revealed that AP enhanced the formation of residual chars at high temperatures, and slightly affected the thermal stability of TPU at high temperatures. The combustion tests indicated that AP affected the burning behavior of TPU. The peak of heat release rate （PHRR）, total heat release （THR） and mass loss rate （MLR） greatly reduced due to the incorporation of AP. The tensile test results showed that both the tensile strength and the elongation at break slightly decreased with the addition of AP. The digital photos and SEM micrographs vitrified that AP facilitated the formation of more compact intumescent char layer. Based on these results mentioned above, the flame-retarding mechanism of AP was discussed. Both the self-charring during the decomposing process of AP and its facilitation to the charring of TPU led to the great improvement in the flame retardancy of TPU.
基金Supported by the National Natural Science Foundation of China (Grant No. 20774016)Heilongjiang Science Fund for Distinguished Young Scholars (Grant No. JC 04-06)
文摘A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR,13C NMR,31P NMR,FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA),differential scanning calorimentry (DSC) and FTIR,while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss,and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions,it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37℃. And the sample hydrolytic degradation still remains at the stage of side groups' break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP),hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%,47% and 47% at 800℃,respectively,probably due to cross-linking between molecules.
基金Supported by the Natural Science Foundation of Guangdong Province,China(No.2017A030307028)the Special Fund for Science and Technology Innovation Strategy of Guangdong Province,China(No.2018A01005)+1 种基金the Yangfan Plan of Guangdong Province,China(No.0003017011)he Research Initiation Foundation of the Lingnan Normal University,China(Nos.ZL1604,ZL1822).
文摘Octyl(triphenylethynyl)silane monomer(OTPES)was synthesized with ethyl bromide,octyltrichlorosilane and phenylethylene by Grignard reaction.The molecular structure was confirmed by FTIR and NMR.The poly[octyl(triphenylethynyl)]silane resin(POTPES)was prepared by thermal polymerization and the corresponding thermal degradation behavior wasstudied by thermogravimetric analysis(TG)combining with model and model-free fitted methods.The dielectric property of resin was also studied by vector network analyzer.The results show that the melt point of OTPES was 50℃ and the processing window was over 236℃.The resin degradation temperature of Td5 occurred over 433℃ and the char yield was over 60%at 800℃.Based on Kissinger,Flynn-Wall-Ozawa,Coats-Redfern,Achar,Vyazovkin-Wight and Tang methods,the reaction activity(E)was 155.51,152.97,150.82,146.02,148.38 and 148.77 kJ/mol,respectively.Dielectric properties analysis displayed that the real part(ε′)and the imaginary part(ε″)of the relative complex permittivity of POTPES was 2.5 and 0.05,respectively,and the dielectric loss tangent was between 0.03 and 0.25.The reflection loss of resin was more than?2.85 dB in all range of 1–5 mm thicknesses and 2–18 GHz frequency,which indicated that POTPES resin was a real wave-transparent resin matrix.
基金Funded by the Program(BG20190227001)of High-end Foreign Experts of the State Administration of Foreign Experts Affairs(SAFEA)the Coal Conversion and New Carbon Materials Hubei Key Laboratory in Wuhan University of Science and Technology(WKDM201909)。
文摘A series of degradable polyesters was synthesized via melt polymerization of 3,6-dioxaoctane-1,8-dioic acid and five different diols,catalyzed by antimony trioxide(Sb_(2)O_(3)).The polymers were characterized by FT-IR and ^(1)H NMR spectroscopy,gel permeation chromatography(GPC)and differential scanning calorimetry(DSC)analysis.The polydispersity index(PDI=M_(w)/M_(n))of the polyesters ranged from 1.55 to 1.99,the weight-average molecular weight(M_(w))from 1.8×10^(4) to 3.2×10^(4) Da,the melting point from 63 to 123℃,and the highest decomposition temperature observed was 363℃.The influence of the structure of the polymer chain on hydrolytic degradability was investigated with tests performed at three different values of pH.The findings obtained provide useful insight for the molecular design and the synthesis of degradable polyesters.
