With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysi...With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.展开更多
This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification wa...This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification was revealed combining thermogravimetric(TG)analysis,Fourier transform infrared spectroscopy,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state 13C nuclear magnetic resonance spectroscopy.Furthermore,crucible coking experiments were also conducted using industrial coal mixture and treated PET with the optimum G(PET300)or raw PET to evaluate the applicability of PET waste in coal-blending coking.According to characterization results of coke reactivity(CR),coke strength after reaction(CSR)indices,TG-related curves,pore volumes,and Raman spectra of the resultant cokes,LTPT could greatly increase the G of PET,and the optimum temperature was 300℃.Specifically,compared with the coke obtained from the blend with PET,the CR of the coke produced from the blend with PET300 decreased by 4.9%,whereas the CSR of the increased by 7.4%,suggesting that LTPT could increase the proportion of PET used for coal-blending coking.The improvement in G is attributed to the changes in C-O/C=O ratio,aliphatic H and aromaticity caused by LTPT.展开更多
In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymeriz...In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.展开更多
The rheological behavior of fumed silica suspensions in polyethylene glycol(PEG) was studied at steady and oscillatory shear stress using AR 2000 stress controlled rheometer. The systems show reversible shear thickeni...The rheological behavior of fumed silica suspensions in polyethylene glycol(PEG) was studied at steady and oscillatory shear stress using AR 2000 stress controlled rheometer. The systems show reversible shear thickening behavior and the shear-thickening behavior can be explained by the clustering mechanism. The viscosity and the degree of shear-thickening of the systems strongly depend on the mass fraction of the silica, the molecular weigh of PEG and the frequency used in the rheological measurement. The silica volume fraction of the systems is 1.16% 3.62%, corresponding to the mass fraction of 4%9%. The shear-thickening taking place in the low volume fraction may contribute to the fractal nature of the silica. At oscillatory shear stress, when the shear stress is less than the critical stress, the storage modulus decreases significantly, meanwhile the loss modulus and the complex viscosity almost remain unchanged; when the shear stress is larger than the critical stress, the storage modulus, the loss modulus and the complex viscosity increase with the increase of shear stress. The loss modulus is larger than the storage modulus in the range of stress studied and both moduli depend on frequency.展开更多
The experimental observations about remarkable influence of the substrates on the isothermal crystallization rate of a high density polyethylene(HDPE) were presented.Two methods were used to characterize the crystalli...The experimental observations about remarkable influence of the substrates on the isothermal crystallization rate of a high density polyethylene(HDPE) were presented.Two methods were used to characterize the crystallization rate:the change of turbidity of the HDPE specimen and the changes of the complex viscosity and storage modulus measured by a rotational rheometer,which gave consistent results showing that the isothermal crystallization rate decreased in sequence as the specimen contacted with aluminum,brass and stainless steel plates,respectively.As to the dominant influence factor,the chemical composition of the substrates can be excluded via insulating the plate by an aluminum foil.Instead,we propose the plate's ability of removing the latent heat of crystallization from the specimen.Rheological measurement is sensitive to the crystallization process.The colloid like model proposed by BOUTAHAR et al for the crystallization of HDPE gives reasonable predictions of the crystallized fraction from the measured storage modulus.展开更多
Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable p...Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable polyethylene glycol with organic monomers, resorcinol and formaldehyde and then subjected to pyrolization at 1 000 ℃. The influences of mass ratio of PEG to the theoretical yield of RF xerogel, m（PEG）/m（RF） and the （relative） molecular mass of PEG on the pore structure and electric double layer capacitance（EDLC） performance of PEG-RF carbon xerogels were investigated. The results show that PEG under different conditions leads to the difference of phase separation structure of the polymer blend and thus the change of pore structure of PEG-RF carbon xerogels. Specific surface area and capacity of PEG-RF carbon xerogels in 30% H2SO4 solution can reach （755 m2/g） and 150 F/g, respectively. Their surface can be fully utilized to form electric double layer. However, the pore structure differences of PEG-RF carbon xerogels result in their different EDLC performances. The distributed capacitance effect increases with decreasing the pore size of PEG-RF carbon xerogels.展开更多
Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilan...Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene （LLDPE） composite, filled with 50% （mass fraction） of MAH modified by 5.0% （mass fraction） of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.展开更多
Low density polyethylene film surface-grafted resorcinol was prepared by a sequential process.Firstly, acrylic acid was grafted to the surface of low density polyethylene by UV photo-grafting.Secondly, the carboxylic ...Low density polyethylene film surface-grafted resorcinol was prepared by a sequential process.Firstly, acrylic acid was grafted to the surface of low density polyethylene by UV photo-grafting.Secondly, the carboxylic groups in poly（acrylic acid） chains were transferred to acyl chloride groups by the reaction of carboxylic groups with thionyl chloride.The stability of acyl chloride groups in several solvents（alcohol, water, acetone, aqueous NaOH and in N2 atmosphere） was investigated, and N2 atmosphere and acetone were appropriate media to protect acyl chloride groups from side reaction.Finally, resorcinol monomer reacted with acyl chloride to append to the poly（acrylic acid）chains at room temperature.FT-IR-ATR was used to characterize the change of carbonyl groups during each step of the grafting process.Furthermore, by the experimental data of gravimetric analysis the grafted resorcinol monomer on the surface of low density polyethylene film was verified to have undergone condensation with acetone further in the resorcinol/acetone solution at 56℃, which might be a useful feature for synthesizing a thermoplastic/thermosetting composition.展开更多
In order to explore the mechanism of improving the surface wettability of low-energy polytetrafluoroethylene(PTFE)by new extended surfactants,five kinds of extended anionic surfactants with different numbers of oxypro...In order to explore the mechanism of improving the surface wettability of low-energy polytetrafluoroethylene(PTFE)by new extended surfactants,five kinds of extended anionic surfactants with different numbers of oxypropylene(PO)and oxyethylene(EO),octadecyl-(PO)_(m)-(EO)_(n)-sodium carboxylate(C_(18)PO_(m)EO_(n)C,m=5,10,15,n=5,10,15),were studied.The surface tension and contact angle of C_(18)PO_(m)EO_(n)C solution with different concentrations were measured,and the adhesion tension,PTFE-water interfacial tension,and adhesion work were calculated.It was found that the extended surfactant molecules adsorb on the surface of the solution and the PTFE-liquid interface simultaneously when the concentration is lower than the critical micelle concentration(cmc),and there was a linear relationship between surface tension and adhesion tension.The adsorption amount of C_(18)PO_(m)EO_(n)C at the PTFE-water interface was significantly lower than that on the surface of the solution.As the concentration increases above cmc,semi-micelle aggregates on the surface of PTFE are formed by C_(18)PO_(m)EO_(n)C molecules through hydrophobic interaction,and the hydrophilic group faces the solution to modify the surface of PTFE with high efficiency.展开更多
A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynami...A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.展开更多
文摘With the aim to effectively depolymerize polyethylene terephthalate(PET)under mild reaction conditions,PET methanolysis and dimethyl terephthalate(DMT)hydrolysis are integrated in a catalyst system.Firstly,methanolysis of PET to DMT is achieved over Cu-Mg-Al oxide catalyst.Next,terephthalic acid(TPA)is prepared by DMT hydrolysis.It is found that hydrolysis of DMT to TPA can be promoted by introducing trace amount of water in this catalyst system.CuO-MgO-4.5Al_2O_(3)catalyst demonstrates the excellent catalytic performance for the depolymerization of PET with high conversion rate and TPA yield(100%and 99.5%,respectively)after reaction at 160℃for 6 h,which provides a new idea for the depolymerization of PET.
基金supported by the National Natural Science Foundation of China(22308006,22278001)the Natural Science Foundation of Anhui Provincial Education Department(KJ2021A0407).
文摘This work proposed a strategy to improve the caking index of polyethylene terephthalate(PET)waste,in which low-temperature pyrolysis treatment(LTPT)was used to depolymerize PET waste.The mechanism of G modification was revealed combining thermogravimetric(TG)analysis,Fourier transform infrared spectroscopy,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state 13C nuclear magnetic resonance spectroscopy.Furthermore,crucible coking experiments were also conducted using industrial coal mixture and treated PET with the optimum G(PET300)or raw PET to evaluate the applicability of PET waste in coal-blending coking.According to characterization results of coke reactivity(CR),coke strength after reaction(CSR)indices,TG-related curves,pore volumes,and Raman spectra of the resultant cokes,LTPT could greatly increase the G of PET,and the optimum temperature was 300℃.Specifically,compared with the coke obtained from the blend with PET,the CR of the coke produced from the blend with PET300 decreased by 4.9%,whereas the CSR of the increased by 7.4%,suggesting that LTPT could increase the proportion of PET used for coal-blending coking.The improvement in G is attributed to the changes in C-O/C=O ratio,aliphatic H and aromaticity caused by LTPT.
基金Project(2016TP1007)supported by the Hunan Provincial Science and Technology Plan,China
文摘In this work,a novel alcohol alkali hydrolysis method was explored for the preparation of terephthalic acid(TPA)from waste polyethylene terephthalate(PET).First,a series of single factor experiments on the depolymerization rate of waste PET bottles and the yield of TPA were conducted to determine the optimized experimental conditions,in terms of reaction time,reaction temperature,dosage of ethylene glycol and sodium bicarbonate,amount of distilled water and stirring rate.Then IR spectra and elemental analysis were carried out for the characterization of obtained product.Under optimal experimental conditions,over 98%PET can be depolymerized into the target product(TPA)and the purity and yield of TPA are over 97%and 94%,respectively.Both the experimental and analytical results support a feasible process for the preparation of TPA from waste PET.It is expected that this alcohol alkali hydrolysis method can promise an effective way for the sustainable recycling of waste PET.
文摘The rheological behavior of fumed silica suspensions in polyethylene glycol(PEG) was studied at steady and oscillatory shear stress using AR 2000 stress controlled rheometer. The systems show reversible shear thickening behavior and the shear-thickening behavior can be explained by the clustering mechanism. The viscosity and the degree of shear-thickening of the systems strongly depend on the mass fraction of the silica, the molecular weigh of PEG and the frequency used in the rheological measurement. The silica volume fraction of the systems is 1.16% 3.62%, corresponding to the mass fraction of 4%9%. The shear-thickening taking place in the low volume fraction may contribute to the fractal nature of the silica. At oscillatory shear stress, when the shear stress is less than the critical stress, the storage modulus decreases significantly, meanwhile the loss modulus and the complex viscosity almost remain unchanged; when the shear stress is larger than the critical stress, the storage modulus, the loss modulus and the complex viscosity increase with the increase of shear stress. The loss modulus is larger than the storage modulus in the range of stress studied and both moduli depend on frequency.
基金Project(20050335050) supported by the Special Foundation of Education Ministry of ChinaProject(10472105) supported by the National Natural Science Foundation of China
文摘The experimental observations about remarkable influence of the substrates on the isothermal crystallization rate of a high density polyethylene(HDPE) were presented.Two methods were used to characterize the crystallization rate:the change of turbidity of the HDPE specimen and the changes of the complex viscosity and storage modulus measured by a rotational rheometer,which gave consistent results showing that the isothermal crystallization rate decreased in sequence as the specimen contacted with aluminum,brass and stainless steel plates,respectively.As to the dominant influence factor,the chemical composition of the substrates can be excluded via insulating the plate by an aluminum foil.Instead,we propose the plate's ability of removing the latent heat of crystallization from the specimen.Rheological measurement is sensitive to the crystallization process.The colloid like model proposed by BOUTAHAR et al for the crystallization of HDPE gives reasonable predictions of the crystallized fraction from the measured storage modulus.
文摘Mesoporous polyethylene glycol-resorcinol and formaldehyde（PEG-RF） carbon xerogels were prepared by a new polymer blend method in which PEG-RF mixed organic xerogels were synthesized by blending thermally unstable polyethylene glycol with organic monomers, resorcinol and formaldehyde and then subjected to pyrolization at 1 000 ℃. The influences of mass ratio of PEG to the theoretical yield of RF xerogel, m（PEG）/m（RF） and the （relative） molecular mass of PEG on the pore structure and electric double layer capacitance（EDLC） performance of PEG-RF carbon xerogels were investigated. The results show that PEG under different conditions leads to the difference of phase separation structure of the polymer blend and thus the change of pore structure of PEG-RF carbon xerogels. Specific surface area and capacity of PEG-RF carbon xerogels in 30% H2SO4 solution can reach （755 m2/g） and 150 F/g, respectively. Their surface can be fully utilized to form electric double layer. However, the pore structure differences of PEG-RF carbon xerogels result in their different EDLC performances. The distributed capacitance effect increases with decreasing the pore size of PEG-RF carbon xerogels.
基金Project(20574020) supported by the National Natural Science Foundation of ChinaProject(20061001) supported by the Opening Project of the Key Laboratory of Polymer Processing Engineering, Ministry of Education, ChinaProject (20060106-2) supported by Guangdong Key Projects
文摘Metal hydroxides （MAH） consisting of magnesium hydroxide and aluminum hydroxide with a mass ratio of 1：2 were surface-modified by y-diethoxyphosphorous ester propyldiethoxymethylsilane, boric acid and diphenylsilanediol in xylene under dibutyl tin dilaurate catalyst at 140 ℃. Phosphorus, silicon and boron elements covalently bonded to metal hydroxide particles were detected by X-ray photoelectron spectroscopy. The degradation behavior of the surface-modified MAH was characterized by thermogravimetric analysis. The results show that linear low density polyethylene （LLDPE） composite, filled with 50% （mass fraction） of MAH modified by 5.0% （mass fraction） of modifiers, passes the V-0 rating of UL-94 test and shows the limited oxygen index of 34%, and its heat release rate and average effective heat combustion in a cone calorimeter measurement decrease obviously; The mechanical properties of MAH can be improved by surface-modification. The uniform dispersion of particles and strong interfacial bonding between particles and matrix are obtained.
文摘Low density polyethylene film surface-grafted resorcinol was prepared by a sequential process.Firstly, acrylic acid was grafted to the surface of low density polyethylene by UV photo-grafting.Secondly, the carboxylic groups in poly（acrylic acid） chains were transferred to acyl chloride groups by the reaction of carboxylic groups with thionyl chloride.The stability of acyl chloride groups in several solvents（alcohol, water, acetone, aqueous NaOH and in N2 atmosphere） was investigated, and N2 atmosphere and acetone were appropriate media to protect acyl chloride groups from side reaction.Finally, resorcinol monomer reacted with acyl chloride to append to the poly（acrylic acid）chains at room temperature.FT-IR-ATR was used to characterize the change of carbonyl groups during each step of the grafting process.Furthermore, by the experimental data of gravimetric analysis the grafted resorcinol monomer on the surface of low density polyethylene film was verified to have undergone condensation with acetone further in the resorcinol/acetone solution at 56℃, which might be a useful feature for synthesizing a thermoplastic/thermosetting composition.
文摘In order to explore the mechanism of improving the surface wettability of low-energy polytetrafluoroethylene(PTFE)by new extended surfactants,five kinds of extended anionic surfactants with different numbers of oxypropylene(PO)and oxyethylene(EO),octadecyl-(PO)_(m)-(EO)_(n)-sodium carboxylate(C_(18)PO_(m)EO_(n)C,m=5,10,15,n=5,10,15),were studied.The surface tension and contact angle of C_(18)PO_(m)EO_(n)C solution with different concentrations were measured,and the adhesion tension,PTFE-water interfacial tension,and adhesion work were calculated.It was found that the extended surfactant molecules adsorb on the surface of the solution and the PTFE-liquid interface simultaneously when the concentration is lower than the critical micelle concentration(cmc),and there was a linear relationship between surface tension and adhesion tension.The adsorption amount of C_(18)PO_(m)EO_(n)C at the PTFE-water interface was significantly lower than that on the surface of the solution.As the concentration increases above cmc,semi-micelle aggregates on the surface of PTFE are formed by C_(18)PO_(m)EO_(n)C molecules through hydrophobic interaction,and the hydrophilic group faces the solution to modify the surface of PTFE with high efficiency.
文摘A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.
