The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the to...The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the toxicity of phthalate esters.In this study,a new,efficient and environmentally friendly plasticizer of hydrogenated rosin dodecyl ester was prepared by an esterification reaction of hydrogenated rosin and dodecanol.The influences of different reaction conditions(including different catalysts,the catalyst concentration,the ratio of the reactants,reaction temperature,and reaction time)on the esterification yield are examined and discussed.Hydrogenated rosin dodecyl ester with 71.8%yield was synthesized under the optimized reaction conditions(1:0.8 molar ratio of rosin to dodecanol,1 mol%tetrabutyl titanate concentration,and 210℃for 6 h).The esterification reaction is a second-order reaction,and kinetic calculations showed that the activation energy is 39.77 KJ·mol^(−1).The structure of the hydrogenated rosin dodecyl ester was confirmed by FT-IR spectroscopy and^(13)C NMR spectrum.Besides,the thermal stability of target product(hydrogenated rosin dodecyl ester)was also tested by thermal gravimetric analysis(TGA),which showed a good thermal stability.展开更多
Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in ...Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor.The conversion achieved nearly 100%within 5 h under the reaction temperature,the mass ratio of catalyst to fatty acid methyl esters(FAMEs),and isobutanol to FAMEs total molar ratio of 180℃,0.4%(mass),and 5.4:1,respectively.In addition,kinetic model of the transesterification reaction was developed at 150–190℃.The calculated activation energy was 48.93 kJ·mol^(-1).Then,the epoxidation of obtained fatty acid isobutyl esters(FABEs)was conducted in the presence of formic acid and hydrogen peroxide.The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate(DOP)and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters(Ep-FAMEs).The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP.In addition,the extraction resistance and migration stability of Ep-FABEs were better than those of EpFAMEs.Overall,the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.展开更多
The phthalate esters such as DMP, DEP, DBP and DEHP in air, soil and plant samples in plastic film greenhouse were clean up with fine silica gel column and determined with HPLC. It was found that the concentrations o...The phthalate esters such as DMP, DEP, DBP and DEHP in air, soil and plant samples in plastic film greenhouse were clean up with fine silica gel column and determined with HPLC. It was found that the concentrations of PEs in air and soil samples in plastic film greenhouse are much higher than those of contrast samples. But concentrations of PEs in plants in plastic film greenhouse are not remarkably affected by the pollution of air and soil.展开更多
This paper described the first example of polyamidoamine dendrimers ester(PAMAM) used as a gel electrolyte with a short-chain polyethylene glycol (MPEG-400) as aplasticizer. The polymer films are solid and sticky. Bac...This paper described the first example of polyamidoamine dendrimers ester(PAMAM) used as a gel electrolyte with a short-chain polyethylene glycol (MPEG-400) as aplasticizer. The polymer films are solid and sticky. Background cyclic voltammetry (CV) shows apotential window between +0.7 and -0.7 V vs. Ag/AgCl. The voltammetry of ferrocene and7,7,8,8-tetracyanoquinodimethane (TCNQ) indicates that diffusion coefficients are in the range of10^(-8) -10^(-9) cm^2/s. Ionic conductivities are approximately 10^(-6) S/cm. Similar films usingdimethyl sulfoxide (DMSO) as a plasticizer instead of MPEG-400 have demonstrated ionicconductivities of 10^(-4) S/cm and reversible voltammetry. However, UV spectropho-tometry shows that70% of the DMSO is lost under vacuum, indicating the difficulty in quantifying the DMSO contentwhen exposed to vacuum.展开更多
Plastic pollution as a global environmental issue has become a research hotspot,among which the removal of inherent plasticizer(e.g.,phthalic acid esters,PAEs)received increasing attention.However,the effects of bioch...Plastic pollution as a global environmental issue has become a research hotspot,among which the removal of inherent plasticizer(e.g.,phthalic acid esters,PAEs)received increasing attention.However,the effects of biochars derived from different feedstocks on the adsorption of PAEs are poorly understood.Thus,the characteristics of biochars derived from six largely produced biomass wastes in China at 400°C,as well as their performance in adsorption of diethyl phthalate(DEP),one of frequently detected PAEs in aqueous environment,were investigated.The results indicated that the variation in feedstock type showed significant changes in the properties(e.g.,porosity,specific surface area,surface functional groups)of biochars,which affected DEP adsorption and desorption.Pseudosecond order and Freundlich models fitted the adsorption data well,and adsorption mechanisms mainly included hydrophobic effect,followed by micropore filling,hydrogen bonding,andπ-πEDA interactions.Adsorption thermodynamics revealed that the adsorption was a spontaneous and exothermic the adsorption capacities of DEP on these biochars slightly decreased with the increasing pH but increased with the increasing ionic strength.Among these biochars,the giant reed biochar with relatively higher DEP adsorption and low desorption exhibited the great efficiency for DEP removal as an environment-friendly sorbent.These results highlighted the significant roles of micropore filling and hydrogen bond in determining adsorption capacity of designed biochars prepared from selecting suitable agricultural straws and wetland plant waste to typical plasticizer.The findings are useful for producing designed biochars from different biomass wastes for plasticizer pollution control.展开更多
Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-p...Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens.However,commercial EFAMEs,even with the highest epoxy value(ca.5.5-5.8%)so far,still suffer from fast leaching from the PVC matrix,burdening the environment and shortening lifespan of the artificial material.Here,we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester.Despite a low epoxy value(3.0%),the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value(5.8%).Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance,the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates,thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.展开更多
基金the financial support From the Open Fund Project of Key Lab.of Biomass Energy and Material,Jiangsu Province(JSBEM201907)the Ordinary University Young Innovative Talents Project of Guangdong Province(2018KQNCX119)+4 种基金Provincial Science and Technology Planning Projects of Guangdong Province(2017A040405055)Guangdong-Hong Kong Cooperation Project(2017A050506055)Guangdong Provincial Education Department Project(Natural Science,2017KZDXM045)Guangzhou major special project for collaborative innovation of industry,University and research(201604020074)the fund project of Yele Science and Technology Innovation(YL201807).
文摘The plasticizer is an important polymer material additive.Non-toxic and environmentally friendly plasticizers are developed recently in order to decrease fossil fuel reserves,serious environmental pollution and the toxicity of phthalate esters.In this study,a new,efficient and environmentally friendly plasticizer of hydrogenated rosin dodecyl ester was prepared by an esterification reaction of hydrogenated rosin and dodecanol.The influences of different reaction conditions(including different catalysts,the catalyst concentration,the ratio of the reactants,reaction temperature,and reaction time)on the esterification yield are examined and discussed.Hydrogenated rosin dodecyl ester with 71.8%yield was synthesized under the optimized reaction conditions(1:0.8 molar ratio of rosin to dodecanol,1 mol%tetrabutyl titanate concentration,and 210℃for 6 h).The esterification reaction is a second-order reaction,and kinetic calculations showed that the activation energy is 39.77 KJ·mol^(−1).The structure of the hydrogenated rosin dodecyl ester was confirmed by FT-IR spectroscopy and^(13)C NMR spectrum.Besides,the thermal stability of target product(hydrogenated rosin dodecyl ester)was also tested by thermal gravimetric analysis(TGA),which showed a good thermal stability.
基金Financial support provided by the National High-tech Research and Development Program of China(2014AA022103)。
文摘Biodiesel was used to prepare epoxidized fatty acid isobutyl esters(Ep-FABEs)as a biobased plasticizer in this work.Transesterification of biodiesel with isobutanol catalyzed by tetrabutyl titanate was carried out in a gas-liquid tower reactor.The conversion achieved nearly 100%within 5 h under the reaction temperature,the mass ratio of catalyst to fatty acid methyl esters(FAMEs),and isobutanol to FAMEs total molar ratio of 180℃,0.4%(mass),and 5.4:1,respectively.In addition,kinetic model of the transesterification reaction was developed at 150–190℃.The calculated activation energy was 48.93 kJ·mol^(-1).Then,the epoxidation of obtained fatty acid isobutyl esters(FABEs)was conducted in the presence of formic acid and hydrogen peroxide.The Ep-FABEs was further analyzed for its plasticizing effectiveness to replace dioctyl phthalate(DOP)and compared with conventional epoxy plasticizer epoxidized fatty acid methyl esters(Ep-FAMEs).The results indicated that the thermal stability and mechanical properties of PVC films with Ep-FABEs plasticizer were significantly improved compared with those plasticized with DOP.In addition,the extraction resistance and migration stability of Ep-FABEs were better than those of EpFAMEs.Overall,the prepared Ep-FABEs via structural modification of biodiesel proved to be a promising biobased plasticizer.
基金We thank the financial support from the National Natural Science Foundation of China
文摘The phthalate esters such as DMP, DEP, DBP and DEHP in air, soil and plant samples in plastic film greenhouse were clean up with fine silica gel column and determined with HPLC. It was found that the concentrations of PEs in air and soil samples in plastic film greenhouse are much higher than those of contrast samples. But concentrations of PEs in plants in plastic film greenhouse are not remarkably affected by the pollution of air and soil.
基金This work was financially supported by the National Natural Science Foundation of China (No. 29875018) the Natural Science Foundation of Gansu Province (No. ZS991-A25-008-Z)the Doctorate Foundation of Northwestern Politech-nical University (No. CX200
文摘This paper described the first example of polyamidoamine dendrimers ester(PAMAM) used as a gel electrolyte with a short-chain polyethylene glycol (MPEG-400) as aplasticizer. The polymer films are solid and sticky. Background cyclic voltammetry (CV) shows apotential window between +0.7 and -0.7 V vs. Ag/AgCl. The voltammetry of ferrocene and7,7,8,8-tetracyanoquinodimethane (TCNQ) indicates that diffusion coefficients are in the range of10^(-8) -10^(-9) cm^2/s. Ionic conductivities are approximately 10^(-6) S/cm. Similar films usingdimethyl sulfoxide (DMSO) as a plasticizer instead of MPEG-400 have demonstrated ionicconductivities of 10^(-4) S/cm and reversible voltammetry. However, UV spectropho-tometry shows that70% of the DMSO is lost under vacuum, indicating the difficulty in quantifying the DMSO contentwhen exposed to vacuum.
基金supported by the Shandong Provincial Major Science and Technology Innovation Project(China)(2019JZZY020302)the National Natural Science Foundation of China(Grant No.22106136)+1 种基金Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(China)(220LH061)National Science Fund for Distinguished Young Scholars of Shandong Province(China)(ZR2021JQ13).
文摘Plastic pollution as a global environmental issue has become a research hotspot,among which the removal of inherent plasticizer(e.g.,phthalic acid esters,PAEs)received increasing attention.However,the effects of biochars derived from different feedstocks on the adsorption of PAEs are poorly understood.Thus,the characteristics of biochars derived from six largely produced biomass wastes in China at 400°C,as well as their performance in adsorption of diethyl phthalate(DEP),one of frequently detected PAEs in aqueous environment,were investigated.The results indicated that the variation in feedstock type showed significant changes in the properties(e.g.,porosity,specific surface area,surface functional groups)of biochars,which affected DEP adsorption and desorption.Pseudosecond order and Freundlich models fitted the adsorption data well,and adsorption mechanisms mainly included hydrophobic effect,followed by micropore filling,hydrogen bonding,andπ-πEDA interactions.Adsorption thermodynamics revealed that the adsorption was a spontaneous and exothermic the adsorption capacities of DEP on these biochars slightly decreased with the increasing pH but increased with the increasing ionic strength.Among these biochars,the giant reed biochar with relatively higher DEP adsorption and low desorption exhibited the great efficiency for DEP removal as an environment-friendly sorbent.These results highlighted the significant roles of micropore filling and hydrogen bond in determining adsorption capacity of designed biochars prepared from selecting suitable agricultural straws and wetland plant waste to typical plasticizer.The findings are useful for producing designed biochars from different biomass wastes for plasticizer pollution control.
基金financial support of this work by National Key Research and Development Program of China(2017YFB0308600)National Natural Science Foundation of China(21878196)Fundamental Research Funds for the Central Universities,China(20826041C4159).
文摘Processing polyvinyl chloride(PVC)artificial material requires plasticizer that softens the PVC coating.Currently,utilizing unsaturated fatty acid methyl esters to obtain epoxidized fatty acid methyl ester(EFAME)bio-plasticizers constitutes an environmentally responsible solution to substitute conventional ortho-phthalates that are endocrine disruptors or probable carcinogens.However,commercial EFAMEs,even with the highest epoxy value(ca.5.5-5.8%)so far,still suffer from fast leaching from the PVC matrix,burdening the environment and shortening lifespan of the artificial material.Here,we report a proof-of-principle demonstration of a new strategy to obtain migration-resistant EFAME that harnesses the midchain hydroxyl of methyl ricinoleate and covalently attachment of a pendant acetate ester.Despite a low epoxy value(3.0%),the engineered bio-plasticizer displays significantly suppressed migration in multiple scenarios compared with one conventional EFAME with much higher epoxy value(5.8%).Circumventing the limit confronting previous strategy that highlights the sole contribution of epoxy value to achievable migration resistance,the rationale herein may provide guidance for designing new EFAMEs with comparable performance to ortho-phthalates,thus bringing the old and oft-maligned PVC artificial material industry one step closer to sustainability.
