The deficiencies of popular phthalate plasticizers(ready migration from a polymer matrix into which they have been incorporated,flammability,environmental pollution,human health risks)have stimulated efforts to develo...The deficiencies of popular phthalate plasticizers(ready migration from a polymer matrix into which they have been incorporated,flammability,environmental pollution,human health risks)have stimulated efforts to develop new effective,nonmigrating,low-cost,nontoxic replacements.In the main,these have been based on readilyavailable,nontoxic biobased precursors.Some,including those prepared from plant oils,have been generated from biomaterials themselves.However,the more numerous and generally more effective have been generated from discrete compounds produced from various biomaterials.Several structural features of effective plasticizers have been recognized.Polar functionality is required to assure compatibility with a wide range of polymeric materials,including poly(vinyl chloride)(PVC),the most heavily plasticized polymer.A branched structure greatly enhances the effectiveness of compounds used as plasticizers.An oligomeric structure may strongly limit or prevent migration from a polymer matrix.Hyperbranched oligomers of defined structure derived from the readilyavailable,inexpensive,nontoxic biomonomers,glycerol and adipic acid contain all these features and are excellent plasticizers.They contain ester functionality,are highly branched,and display a large number of end groups,all of which contribute to their effectiveness as plasticizers.展开更多
In this study,3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate(ECC)and refined Camellia oleifera seed oil(RCOSO)obtained from saponification and acidified hydrolysis has been used as raw materials to perform ...In this study,3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate(ECC)and refined Camellia oleifera seed oil(RCOSO)obtained from saponification and acidified hydrolysis has been used as raw materials to perform ring-opening reactions for the preparation of cyclohexyl acrylate derivative(CAR).The structure of the synthesized product was characterized using infrared spectroscopy,Raman spectroscopy,and nuclear magnetic resonance spectroscopy.CAR was employed as a plasticizer to produce modified polyvinyl chloride(PVC)films,dioctyl phthalate plasticizer(DOP)used in reference samples to investigate the influence of different plasticizer molecular structures on the properties of PVC films.Observation suggested that(1)CAR plasticizer was successfully synthesized;(2)CAR can interact with PVC,exhibiting good compatibility;(3)PVC films contain CAR showed improved thermal stability,hydrophilicity,and tensile strength.Therefore,CAR has the potential to replace DOP as a plasticizer for PVC.展开更多
Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitati...Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitation.To address this issue,conventional plasticizer,dioctyl adipate(DOA),is replaced by reactive one,castor oil(CO).In addition,three different types of HTPB were used to obtain propellants with designed viscoelastic and mechanical properties.The CO increased propellants viscosity,without a significant impact on the propellant processability,regardless to the type of prepolymer.Conversely,mechanical properties were different depending on the type of resin,which were further analyzed by gel permeation chromatography(GPC).Addition of CO formed a denser polymer network and shifted T_(g) to higher values,compared to the compositions with DOA.The tensile strength of CO-containing propellants was lower at +20℃ and +50℃ compared to the reference compositions,while the strain at maximum load and strain at break were significantly increased with pronounced plastic deformation,especially for samples at -30℃.The inclusion of CO in the propellants composition gives more room for adjusting a wide range of mechanical properties.展开更多
Cellulose acetate(CA)is an important cellulose derivative that can undergo thermoplas-tic processing.Plasticizers can form stable hydrogen bonds with CA molecular chains,reducing intermolecular and intramolecular inte...Cellulose acetate(CA)is an important cellulose derivative that can undergo thermoplas-tic processing.Plasticizers can form stable hydrogen bonds with CA molecular chains,reducing intermolecular and intramolecular interactions,and play an important role in the melting processing of CA.In recent years,environmentally friendly plasticizers that are natural,non-toxic,odorless,low dissolution,and low migration have received increas-ing attention in plastic processing.This article reviews the research progress of environ-mentally friendly plasticizers such as natural plasticizers,ionic liquid plasticizers,citrate plasticizers,and polyethylene glycol plasticizers in the processing of cellulose acetate,and looks forward to the application prospects of environmentally friendly plasticizers.展开更多
Soil microbial fuel cells(MFCs),a novel ecosystem technology,have recently been intensively studied for antibiotic-polluted soils.However,actual agricultural soils are always contaminated by mixed pollutants,especiall...Soil microbial fuel cells(MFCs),a novel ecosystem technology,have recently been intensively studied for antibiotic-polluted soils.However,actual agricultural soils are always contaminated by mixed pollutants,especially plasticizers from extensively used agricultural plastic films.The aim of this study was to investigate the effects of di-2-ethylhexyl phthalate(DEHP),a representative plasticizer in soil,on the removal of sulfadiazine(SDZ),a frequently detected antibiotic in natural environments,and antibiotic resistance genes(ARGs)and microbial community in soil MFCs.Soil MFCs maintained a good antibiotic removal ability even under the influence of residual DEHP and achieved a higher removal performance at higher DEHP concentrations due to enhanced power generation.Specifically,a higher DEHP concentration had a favorable effect on antibiotic removal in soil MFCs,with the SDZ concentration decreased in both the upper and lower layers(from 4.867±0.221 to 0.268±0.021 and 0.293±0.047 mg kg^(-1),respectively)of polluted soils.Moreover,a high DEHP concentration significantly promoted the abundance of bacteria associated with electricity generation compared with a lower DEHP concentration,resulting in the promotion of extracellular electron transfer and enhancing SDZ degradation.The increased ARG abundance may be caused by the enrichment of ARG potential hosts brought about by high DEHP concentration,likely due to the increased conjugative transfer frequencies of plasmid RP4 by decreasing cell membrane permeability and increasing reactive oxygen species content.The results revealed the ecological risk of residual DEHP in soil that promotes ARG transmission in soil MFCs,although it has the potential to reduce SDZ toxicity through horizontal gene transfer.We also highlight concerns regarding the management of antibiotics and plasticizers in soil.The negative effects of plasticizers on antibiotic removal should be carefully evaluated when using soil MFCs for the in-situ remediation of antibiotic-contaminated soil.展开更多
Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cyc...Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cycling rate limitation.Herein,a new strategy is proposed based on a quantum dots(QDs)/PMS system.Co-ZnS QDs are synthesized by a water phase coprecipitation method.The inequivalent lattice-doping of Co for Zn leads to the generation of surface sulfur vacancies(SVs),which modulates the surface of the catalyst to form an electronic nonequilibrium surface.Astonishingly,the plasticizer micropollutants can be completely degraded within only tens of seconds in the Co-Zn S QDs/PMS system due to this type of surface modulation.The interfacial reaction mechanism is revealed that pollutants tend to be adsorbed on the cobalt metal sites as the electron donors,where the internal electrons of pollutants are captured by the metal species and transferred to the surface SVs.Meanwhile,PMS adsorbed on the SVs is reduced to radicals by capturing electrons,achieving effective electron recovery.Dissolved oxygen(DO)molecules are also easily attracted to catalyst defects and are reduced to O_(2)^(·-),further promoting the degradation of pollutants.展开更多
Geminal dinitropropyl ester plasticizers(DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane ...Geminal dinitropropyl ester plasticizers(DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane chain parts, and systematically investigate their structure-property relationships.Results show that DNPEPs have impact sensitivities all higher than 25.2 J, thermal decomposition temperatures all higher than 254 ℃, and glass transition temperatures(T_(g)) lower than-90 ℃.Furthermore, the effects of DNPEPs as plasticizer are studied on hydroxyl terminated polybutadiene(HTPB) in detail, including the viscosity, glass transition temperatures and others. It is noteworthy that 2,2-dinitropropyl nonanoate(DNPNc) among these DNPEPs exhibits the most expected simultaneous tuning effects on both viscosity and T_(g) of HTPB systems, providing favorable potentials to replace the conventional plastizers as dioctyl sebacate(DOS) in the HTPB based propellants and explosives.展开更多
The inhibition and its mechanism of sodium tripolyphosphate （STP） composited with super plasticizers （SPs） on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-r...The inhibition and its mechanism of sodium tripolyphosphate （STP） composited with super plasticizers （SPs） on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, electronic probe micro analysis （EPMA）, scanning electron microscopy （SEM） and differential scanning calorimeter （DSC） measurements. The experimental results show that compared with STP addition, compositing STP with polycarboxylate （PC） plasticizer, the final setting time is prolonged from 0.5h to 2hs. While formulating STP with naphthalene-based plasticizer （NAP） or sulfonate melamine formaldehyde plasticizer （SMF）, the final setting time is reduced to quarter of an hour. Similar changes can also be found in the rate of exothermic hydration and hydration degree. Formulating STP with suitable addition of PC can enhance the strength, while compositing STP and NAP or SMF weakens the strength. Besides, adding STP or STP and SMF, obvious movement （more than 1ev） of binding energy of Ca2p1/2 and Ca2p3/2 is detected. Compared with STP addition, content of the characteristic element （P） of STP is cut down form 1.1% to 0.49% by compositing STP with SMF. Furthermore, as hydration age increases, hydration inhibition in the presence of admixtures weakens and even disappears within 56 h.展开更多
In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of...In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope（SEM）native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.展开更多
An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was c...An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was confirmed and its physico chemical properties were evaluated.PVC/(ESBO&ECO)blends were prepared by melt mixing and compression molded into sheets.The specimens were evaluated for tensile properties,impact strength and hardness.While the tensile strength did not vary much,the elongation reduced with the replacement of ESBO with ECO.Dynamic mechanical studies revealed that the glass transition temperature increased with incorporation of ECO,however,the storage modulus was not altered much.Replacing 20%of ESBO with ECO resulted in blends with desired thermal and mechanical properties without affecting the processability of PVC.展开更多
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
The effects of the plasticizer poly(ethylene glycol)(PEG)on crystallization properties of equimolar poly(L-lactide)(PLLA)/poly(D-lactide)(PDLA)blends were investigated.Forma-tion of the stereocomplex-type poly(lactide...The effects of the plasticizer poly(ethylene glycol)(PEG)on crystallization properties of equimolar poly(L-lactide)(PLLA)/poly(D-lactide)(PDLA)blends were investigated.Forma-tion of the stereocomplex-type poly(lactide acid)(sc-PLA)crystallites was confirmed by Wide-angle X-ray diffraction(WAXD)and differential scanning calorimetry(DSC)analyses.Sc-PLA crystallites without any homochiral poly(lactide acid)(hc-PLA)formed,as the result of the incorporation of the plasticizer PEG(more than or equal to 10%(wt))at a processing temperature(240℃).More-over,when the Mw of PEG reached 1000 g·mol^(-1),the crystal-lizability of stereocomplex crystallites was the best.Isothermal crystallization kinetics further revealed that PEG could accelerate the crystallization rate of sc-PLA,with the optimum crystallization kinetic parameters being obtained at 10%(wt)PEG.Several crys-tallization kinetics equations were applied to describe the effect of PEG on the crystallization behavior of sc-PLA.The influence of PEG on the spherocrystal morphologies of sc-PLA was also inves-tigated using polarized optical microscopy.展开更多
Ethylene glycol, glycerol, sorbitol, formamide, and urea were used as plasticizers for the preparation of thermoplastic starch（TPS） from corn starch. The properties of TPS were tested by analysis method. The results...Ethylene glycol, glycerol, sorbitol, formamide, and urea were used as plasticizers for the preparation of thermoplastic starch（TPS） from corn starch. The properties of TPS were tested by analysis method. The results showed that TPSs were more highly plasticized with amines than alcohols. For the same type of plasticizer, the degree of plasticization decreased as the molecular weight of plasticizer increased. The relationship between plasticization degree and TPS properties was characterized and described by mechanical properties and water absorption. The experimental results showed that when the degree of plasticization increased, the tensile strength decreased and the elongation at breakage and water absorption increased.展开更多
In order to improve the properties of rice straw fiber film, one factor contrast test method was employed. Plasticizer type was chosen as input variable, dry tension strength and elongation, wet tension strength and e...In order to improve the properties of rice straw fiber film, one factor contrast test method was employed. Plasticizer type was chosen as input variable, dry tension strength and elongation, wet tension strength and elongation, bursting strength and tearing strength were chosen as indexes. The results showed that there were significant differences among the means of dry tension strength, dry elongation and bursting strength of different plasticizers; there were not significant differences among the means of wet tension strength, wet elongation and tearing strength of different plasticizers; for dry tension strength and elongation, glycerol had a significant difference with sorbitol and PEG, no significant difference was observed between sorbitol and PEG, dry tension strength added glycerol had been reduced 6.8% compared with that added sorbitol, reduced 9.5% compared with that added PEG; elongation had been improved 6.1% and 9.4%, respectively; for bursting strength, sorbitol had a significant difference with glycerol and PEG, no significant difference was observed between glycerol and PEG; bursting strength added glycerol and added PEG had been improved 6.9% and 5.6%, respectively compared with that of the added sorbitol. The results provided a theoretical reference for further improving the straw fiber film manufacturing process.展开更多
Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was inves...Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.展开更多
The loss of adhesion between the propellant and insulator is one of the most important problems in solid propellant motors due to migration of plasticizer to interface of propellant and insulator. In this work, the po...The loss of adhesion between the propellant and insulator is one of the most important problems in solid propellant motors due to migration of plasticizer to interface of propellant and insulator. In this work, the polyurethane (PU) binder containing DOP plasticizer was used as a polymeric matrix and β-cyclodextrin (β-CD) was applied as inhibitor agent to prevent plasticizer migration from the PU matrix into the ethylene propylene diene monomer (EPDM) substrate. To increase the compatibility of β-CD and PU matrix, a derivative of β-CD has been synthesized using toluene diisocyanate (β-CD-TDI). The synthesized derivative was characterized by MALDI-MS and FTIR-ATR analyses. FTIR-ATR results confirmed the formation of bonding between β-CD and the polymeric network while the MALDIMS results showed that the synthesized derivative contained two β-CD and 7 TDI molecules bonded to β-CD. Investigation of the mechanical properties of PU modified by β-CD-TDI showed a decrease in tensile strength and an increase in elongation at break with increasing β-CD-TDI content. DMTA results showed a decrement in crosslinking density by increasing the β-CD-TDI content. Also, to investigate plasticizer migration, extraction of the DOP plasticizer from samples was performed using dichloromethane solvent and its concentration was measured by gas chromatography. The results of migration evaluation after four months showed that using β-CD as an inhibitor agent in the PU binder could prevent the migration of plasticizer to EPDM substrate.展开更多
in this paper, ethylenebisformamide was synthesized and used as a novel plasticizer for cornstarch to prepare thermoplastic starch （TPS）. FT-IR expressed that ethylenebisformamide formed stronger and stable hydrogen...in this paper, ethylenebisformamide was synthesized and used as a novel plasticizer for cornstarch to prepare thermoplastic starch （TPS）. FT-IR expressed that ethylenebisformamide formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch. X-ray diffraction （XRD） showed that the typical A-style crystallinity in the native starch has been destructed. By scanning electron microscope （SEM） native cornstarch granules were proved to transfer to a homogeneous system. After being stored for one week at RH=33%, the mechanical properties of EPTPS was also studied. The elongation reached to 264% utmost. As a novel plasticizer, ethylenebisformamide would be practical to extend TPS application scopes.展开更多
Cellulose diacetate(CDA)can be melt processed to produce numerous and widely-used plastic products.However,due to the high glass transition temperature(Tg)of CDA,the addition of up to 30 wt%of micromolecular plasticiz...Cellulose diacetate(CDA)can be melt processed to produce numerous and widely-used plastic products.However,due to the high glass transition temperature(Tg)of CDA,the addition of up to 30 wt%of micromolecular plasticizers is indispensable,which significantly reduces the dimensional stability and raises safety concerns from the migration of plasticizers.In this work,a series of CDA-graft poly(lactic acid)(CDA-g-PLA)copolymers were synthesized by ring-opening polymerization of lactide onto the hydroxyI groups of CDA.The resultant CDA-g-PLA copolymers possess adjustable degrees of substitution(DSpua)and side chain length(DPpLa)by controlling the reaction time and feed ratio.The Tgs and thermal flow temperatures(Ts)of CDA-g-PLA strongly depend on DPpA such as the Tgs decrease linearly with the increase of DPA.The CDA-g-PLA copolymers with the DPLA of 3-9 can be directly processed to transparent plastics by melt processing without any external plasticizers,because of their low Tfs of 170-215℃.More impressively.the CDA-g PLA can act as the macromolecular plasticizer.The obtained CDA/CDA-g-PLA has higher storage modulus,flexural modulus and Young's modulus than the commercial CDA plasticized with triethyl citrate.In addition,the CDA/CDA-g PLA exhibits high dimensional stabilty and anti-migration property.During a long term treatment at 80℃ and 60%humidity,the CDA/CDA-g-PLA can retain the initial shape.Therefore,this work not only proposes a facile method for achieving a direct thermoplastic processing of CDA,but also provides a macromolecular plasticizer for CDA to make lightweight,stable and safer biobased thermoplastics.展开更多
In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distri...In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distribution of the third composition in two phases plays a very important role in controlling viscosity ratio and particle size. When DOP was used as the plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduced due to the transference of DOP into PS phase. When polycaprolactone (PCL) was used as the plasticizer of PVC in the same blends, the particle size of PVC could be descreased obviously because PCL does not migrate to PS phase.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
文摘The deficiencies of popular phthalate plasticizers(ready migration from a polymer matrix into which they have been incorporated,flammability,environmental pollution,human health risks)have stimulated efforts to develop new effective,nonmigrating,low-cost,nontoxic replacements.In the main,these have been based on readilyavailable,nontoxic biobased precursors.Some,including those prepared from plant oils,have been generated from biomaterials themselves.However,the more numerous and generally more effective have been generated from discrete compounds produced from various biomaterials.Several structural features of effective plasticizers have been recognized.Polar functionality is required to assure compatibility with a wide range of polymeric materials,including poly(vinyl chloride)(PVC),the most heavily plasticized polymer.A branched structure greatly enhances the effectiveness of compounds used as plasticizers.An oligomeric structure may strongly limit or prevent migration from a polymer matrix.Hyperbranched oligomers of defined structure derived from the readilyavailable,inexpensive,nontoxic biomonomers,glycerol and adipic acid contain all these features and are excellent plasticizers.They contain ester functionality,are highly branched,and display a large number of end groups,all of which contribute to their effectiveness as plasticizers.
基金support from the Scarce and Quality Economic Forest Engineering Technology Research Center(2022GCZX002)the Key Lab.of Biomass Energy and Material,Jiangsu Province(Grant No.JSBEM-S-202305)the Forestry Scientific Research Monitoring Project of Guangdong Province(2025KJXM01).
文摘In this study,3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate(ECC)and refined Camellia oleifera seed oil(RCOSO)obtained from saponification and acidified hydrolysis has been used as raw materials to perform ring-opening reactions for the preparation of cyclohexyl acrylate derivative(CAR).The structure of the synthesized product was characterized using infrared spectroscopy,Raman spectroscopy,and nuclear magnetic resonance spectroscopy.CAR was employed as a plasticizer to produce modified polyvinyl chloride(PVC)films,dioctyl phthalate plasticizer(DOP)used in reference samples to investigate the influence of different plasticizer molecular structures on the properties of PVC films.Observation suggested that(1)CAR plasticizer was successfully synthesized;(2)CAR can interact with PVC,exhibiting good compatibility;(3)PVC films contain CAR showed improved thermal stability,hydrophilicity,and tensile strength.Therefore,CAR has the potential to replace DOP as a plasticizer for PVC.
基金the support of this research from the Serbian Ministry of Education,Science and Technological Development(Grant No.451-03-68/2023-14/200325)Ministry of Defense(Grant No.VA-TT/1/22-24)。
文摘Conventional plasticizers deteriorate mechanical and viscoelastic properties of the propellants due to their migration upon aging and long-term storage,which affects reliability and safety properties during exploitation.To address this issue,conventional plasticizer,dioctyl adipate(DOA),is replaced by reactive one,castor oil(CO).In addition,three different types of HTPB were used to obtain propellants with designed viscoelastic and mechanical properties.The CO increased propellants viscosity,without a significant impact on the propellant processability,regardless to the type of prepolymer.Conversely,mechanical properties were different depending on the type of resin,which were further analyzed by gel permeation chromatography(GPC).Addition of CO formed a denser polymer network and shifted T_(g) to higher values,compared to the compositions with DOA.The tensile strength of CO-containing propellants was lower at +20℃ and +50℃ compared to the reference compositions,while the strain at maximum load and strain at break were significantly increased with pronounced plastic deformation,especially for samples at -30℃.The inclusion of CO in the propellants composition gives more room for adjusting a wide range of mechanical properties.
文摘Cellulose acetate(CA)is an important cellulose derivative that can undergo thermoplas-tic processing.Plasticizers can form stable hydrogen bonds with CA molecular chains,reducing intermolecular and intramolecular interactions,and play an important role in the melting processing of CA.In recent years,environmentally friendly plasticizers that are natural,non-toxic,odorless,low dissolution,and low migration have received increas-ing attention in plastic processing.This article reviews the research progress of environ-mentally friendly plasticizers such as natural plasticizers,ionic liquid plasticizers,citrate plasticizers,and polyethylene glycol plasticizers in the processing of cellulose acetate,and looks forward to the application prospects of environmentally friendly plasticizers.
基金supported by the National Natural Science Foundation of China(Nos.42477014 and 52070101)Huixiang Wang would like to acknowledge the Postgraduate Research Practice Innovation Program of Jiangsu Province,China(No.181200003023218)。
文摘Soil microbial fuel cells(MFCs),a novel ecosystem technology,have recently been intensively studied for antibiotic-polluted soils.However,actual agricultural soils are always contaminated by mixed pollutants,especially plasticizers from extensively used agricultural plastic films.The aim of this study was to investigate the effects of di-2-ethylhexyl phthalate(DEHP),a representative plasticizer in soil,on the removal of sulfadiazine(SDZ),a frequently detected antibiotic in natural environments,and antibiotic resistance genes(ARGs)and microbial community in soil MFCs.Soil MFCs maintained a good antibiotic removal ability even under the influence of residual DEHP and achieved a higher removal performance at higher DEHP concentrations due to enhanced power generation.Specifically,a higher DEHP concentration had a favorable effect on antibiotic removal in soil MFCs,with the SDZ concentration decreased in both the upper and lower layers(from 4.867±0.221 to 0.268±0.021 and 0.293±0.047 mg kg^(-1),respectively)of polluted soils.Moreover,a high DEHP concentration significantly promoted the abundance of bacteria associated with electricity generation compared with a lower DEHP concentration,resulting in the promotion of extracellular electron transfer and enhancing SDZ degradation.The increased ARG abundance may be caused by the enrichment of ARG potential hosts brought about by high DEHP concentration,likely due to the increased conjugative transfer frequencies of plasmid RP4 by decreasing cell membrane permeability and increasing reactive oxygen species content.The results revealed the ecological risk of residual DEHP in soil that promotes ARG transmission in soil MFCs,although it has the potential to reduce SDZ toxicity through horizontal gene transfer.We also highlight concerns regarding the management of antibiotics and plasticizers in soil.The negative effects of plasticizers on antibiotic removal should be carefully evaluated when using soil MFCs for the in-situ remediation of antibiotic-contaminated soil.
基金financially supported by the National Natural Science Foundation of China(Nos.52070046,52122009,51808140and 51838005)the Introduced of Innovative R&D Team Project under the“Pearl River Talent Recruitment Program”of Guangdong Province(No.2019ZT08L387)+1 种基金the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme(Young Scholar)the support from the BL14W1beamline of Shanghai Synchrotron Radiation Facility(SSRF,China)。
文摘Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cycling rate limitation.Herein,a new strategy is proposed based on a quantum dots(QDs)/PMS system.Co-ZnS QDs are synthesized by a water phase coprecipitation method.The inequivalent lattice-doping of Co for Zn leads to the generation of surface sulfur vacancies(SVs),which modulates the surface of the catalyst to form an electronic nonequilibrium surface.Astonishingly,the plasticizer micropollutants can be completely degraded within only tens of seconds in the Co-Zn S QDs/PMS system due to this type of surface modulation.The interfacial reaction mechanism is revealed that pollutants tend to be adsorbed on the cobalt metal sites as the electron donors,where the internal electrons of pollutants are captured by the metal species and transferred to the surface SVs.Meanwhile,PMS adsorbed on the SVs is reduced to radicals by capturing electrons,achieving effective electron recovery.Dissolved oxygen(DO)molecules are also easily attracted to catalyst defects and are reduced to O_(2)^(·-),further promoting the degradation of pollutants.
基金financial support of the National Natural Science Foundation of China (21875185)。
文摘Geminal dinitropropyl ester plasticizers(DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane chain parts, and systematically investigate their structure-property relationships.Results show that DNPEPs have impact sensitivities all higher than 25.2 J, thermal decomposition temperatures all higher than 254 ℃, and glass transition temperatures(T_(g)) lower than-90 ℃.Furthermore, the effects of DNPEPs as plasticizer are studied on hydroxyl terminated polybutadiene(HTPB) in detail, including the viscosity, glass transition temperatures and others. It is noteworthy that 2,2-dinitropropyl nonanoate(DNPNc) among these DNPEPs exhibits the most expected simultaneous tuning effects on both viscosity and T_(g) of HTPB systems, providing favorable potentials to replace the conventional plastizers as dioctyl sebacate(DOS) in the HTPB based propellants and explosives.
基金Funded by the Major State Basic Research Development Program of China (973 Program) (No. 2009CB623104)the National Technology R&D Program for the 11th Five-year Plan (No. 2006BAJ05B03)
文摘The inhibition and its mechanism of sodium tripolyphosphate （STP） composited with super plasticizers （SPs） on hydration of α-calcium sulfate hemihydrate were studied by setting time, strength, hydration heat, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, electronic probe micro analysis （EPMA）, scanning electron microscopy （SEM） and differential scanning calorimeter （DSC） measurements. The experimental results show that compared with STP addition, compositing STP with polycarboxylate （PC） plasticizer, the final setting time is prolonged from 0.5h to 2hs. While formulating STP with naphthalene-based plasticizer （NAP） or sulfonate melamine formaldehyde plasticizer （SMF）, the final setting time is reduced to quarter of an hour. Similar changes can also be found in the rate of exothermic hydration and hydration degree. Formulating STP with suitable addition of PC can enhance the strength, while compositing STP and NAP or SMF weakens the strength. Besides, adding STP or STP and SMF, obvious movement （more than 1ev） of binding energy of Ca2p1/2 and Ca2p3/2 is detected. Compared with STP addition, content of the characteristic element （P） of STP is cut down form 1.1% to 0.49% by compositing STP with SMF. Furthermore, as hydration age increases, hydration inhibition in the presence of admixtures weakens and even disappears within 56 h.
文摘In this paper,aliphatic amidediol was synthesized and mixed with glycerol used as a plasticizer for preparing thermoplastic starch（AGPTPS）.The yield of aliphatic amidediol was 91%.FF-IR expressed that the mixture of aliphatic amidediol and glycerol formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch.By scanning electron microscope（SEM）native cornstarch granules were proved to transfer to a homogeneous continuous system.After being stored for a period time at room temperature,the mechanical properties of AGPTPS were also studied.As a mixed plasticizer,aliphatic amidediol and glycerol would be practical to extend TPS application scopes.
基金Sukanya Satapathy wishes to acknowledge Department of Science and Technology,Government of India,Women Scientists Scheme[Grant No.SR/WOS-A/CS-36/2016(G)]corresponding author Aruna Palanisamy wishes to acknowledge Ministry of environment,forests and climate change(Grant No.F.No.1-2/2013-CT)the funding(manuscript communication number:IICT/Pubs/2019/065).
文摘An acidic cation exchange resin has been used to prepare epoxidised castor oil(ECO)which was used as a co-plasticizer with epoxidised soyabean oil(ESBO)for processing polyvinyl chloride(PVC).The structure of ECO was confirmed and its physico chemical properties were evaluated.PVC/(ESBO&ECO)blends were prepared by melt mixing and compression molded into sheets.The specimens were evaluated for tensile properties,impact strength and hardness.While the tensile strength did not vary much,the elongation reduced with the replacement of ESBO with ECO.Dynamic mechanical studies revealed that the glass transition temperature increased with incorporation of ECO,however,the storage modulus was not altered much.Replacing 20%of ESBO with ECO resulted in blends with desired thermal and mechanical properties without affecting the processability of PVC.
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Supported by the National Natural Science Foundation of China(51403160)the Opening Project of Hubei Key Laboratory Biomass Fibers and Eco-dyeing&Finishing(STRZ2017009)
文摘The effects of the plasticizer poly(ethylene glycol)(PEG)on crystallization properties of equimolar poly(L-lactide)(PLLA)/poly(D-lactide)(PDLA)blends were investigated.Forma-tion of the stereocomplex-type poly(lactide acid)(sc-PLA)crystallites was confirmed by Wide-angle X-ray diffraction(WAXD)and differential scanning calorimetry(DSC)analyses.Sc-PLA crystallites without any homochiral poly(lactide acid)(hc-PLA)formed,as the result of the incorporation of the plasticizer PEG(more than or equal to 10%(wt))at a processing temperature(240℃).More-over,when the Mw of PEG reached 1000 g·mol^(-1),the crystal-lizability of stereocomplex crystallites was the best.Isothermal crystallization kinetics further revealed that PEG could accelerate the crystallization rate of sc-PLA,with the optimum crystallization kinetic parameters being obtained at 10%(wt)PEG.Several crys-tallization kinetics equations were applied to describe the effect of PEG on the crystallization behavior of sc-PLA.The influence of PEG on the spherocrystal morphologies of sc-PLA was also inves-tigated using polarized optical microscopy.
基金Funded by the Fundamental Research Funds for the Central Universities(DL13CB13)the China Postdoctoral Science Foundation Funded Project(No.2014M550178)the National Natural Science Foundation of China(No.31200442)
文摘Ethylene glycol, glycerol, sorbitol, formamide, and urea were used as plasticizers for the preparation of thermoplastic starch（TPS） from corn starch. The properties of TPS were tested by analysis method. The results showed that TPSs were more highly plasticized with amines than alcohols. For the same type of plasticizer, the degree of plasticization decreased as the molecular weight of plasticizer increased. The relationship between plasticization degree and TPS properties was characterized and described by mechanical properties and water absorption. The experimental results showed that when the degree of plasticization increased, the tensile strength decreased and the elongation at breakage and water absorption increased.
基金Supported by the Fund of Science and Technology Research Project of the 12th Five-year Plan(2012BAD32B02-5)
文摘In order to improve the properties of rice straw fiber film, one factor contrast test method was employed. Plasticizer type was chosen as input variable, dry tension strength and elongation, wet tension strength and elongation, bursting strength and tearing strength were chosen as indexes. The results showed that there were significant differences among the means of dry tension strength, dry elongation and bursting strength of different plasticizers; there were not significant differences among the means of wet tension strength, wet elongation and tearing strength of different plasticizers; for dry tension strength and elongation, glycerol had a significant difference with sorbitol and PEG, no significant difference was observed between sorbitol and PEG, dry tension strength added glycerol had been reduced 6.8% compared with that added sorbitol, reduced 9.5% compared with that added PEG; elongation had been improved 6.1% and 9.4%, respectively; for bursting strength, sorbitol had a significant difference with glycerol and PEG, no significant difference was observed between glycerol and PEG; bursting strength added glycerol and added PEG had been improved 6.9% and 5.6%, respectively compared with that of the added sorbitol. The results provided a theoretical reference for further improving the straw fiber film manufacturing process.
基金This work was subsidized for improving medical service and security capacity in 2019“national survey of traditional Chinese medicine resources”(Financial Society[2019]Number 39).
文摘Herein,epoxidized soybean oil methyl ester(ESOM)plasticizer was synthesized for the preparation of plasticized poly(vinyl chloride)(PVC)films by the alcoholysis and epoxidation.The chemical structure of ESOM was investigated by infrared spectrum and 1 H nuclear magnetic resonance.The effect of content of ESOM and petroleum based plasticizer di-2-ethylhexyl phthalate(DEHP)on the performance of plasticized PVC films was studied.The result showed that substituting DEHP with ESOM can improve the thermal stability of plasticized PVC films.When the weight ratio of ESOM and PVC is fixed at 1:2,plasticized PVC film presents higher elongation at break(350.8%vs.345.1%)and lower tensile strength(14.21 MPa vs.15.8 MPa)compared with PVC plasticized with DEHP.ESOM showed less weight loss than DEHP in all solvents.The excellent migration resistance of ESOM is helpful to improve stability of plasticized PVC films.In all,the obtained bio-based plasticizer will be potential to replace petroleum based plasticizer DEHP in flexible PVC materials.
文摘The loss of adhesion between the propellant and insulator is one of the most important problems in solid propellant motors due to migration of plasticizer to interface of propellant and insulator. In this work, the polyurethane (PU) binder containing DOP plasticizer was used as a polymeric matrix and β-cyclodextrin (β-CD) was applied as inhibitor agent to prevent plasticizer migration from the PU matrix into the ethylene propylene diene monomer (EPDM) substrate. To increase the compatibility of β-CD and PU matrix, a derivative of β-CD has been synthesized using toluene diisocyanate (β-CD-TDI). The synthesized derivative was characterized by MALDI-MS and FTIR-ATR analyses. FTIR-ATR results confirmed the formation of bonding between β-CD and the polymeric network while the MALDIMS results showed that the synthesized derivative contained two β-CD and 7 TDI molecules bonded to β-CD. Investigation of the mechanical properties of PU modified by β-CD-TDI showed a decrease in tensile strength and an increase in elongation at break with increasing β-CD-TDI content. DMTA results showed a decrement in crosslinking density by increasing the β-CD-TDI content. Also, to investigate plasticizer migration, extraction of the DOP plasticizer from samples was performed using dichloromethane solvent and its concentration was measured by gas chromatography. The results of migration evaluation after four months showed that using β-CD as an inhibitor agent in the PU binder could prevent the migration of plasticizer to EPDM substrate.
文摘in this paper, ethylenebisformamide was synthesized and used as a novel plasticizer for cornstarch to prepare thermoplastic starch （TPS）. FT-IR expressed that ethylenebisformamide formed stronger and stable hydrogen bond with starch molecules compared to the native cornstarch. X-ray diffraction （XRD） showed that the typical A-style crystallinity in the native starch has been destructed. By scanning electron microscope （SEM） native cornstarch granules were proved to transfer to a homogeneous system. After being stored for one week at RH=33%, the mechanical properties of EPTPS was also studied. The elongation reached to 264% utmost. As a novel plasticizer, ethylenebisformamide would be practical to extend TPS application scopes.
基金This work was finacially supported by the National Key Research and Development Program of China(No.2017YFA0403103)the Key Programs of the Chinese Academy of Sciences(No.ZDRW-CN-2018-2)the Youth Innovation Promotion Association CAS(No.2018040).
文摘Cellulose diacetate(CDA)can be melt processed to produce numerous and widely-used plastic products.However,due to the high glass transition temperature(Tg)of CDA,the addition of up to 30 wt%of micromolecular plasticizers is indispensable,which significantly reduces the dimensional stability and raises safety concerns from the migration of plasticizers.In this work,a series of CDA-graft poly(lactic acid)(CDA-g-PLA)copolymers were synthesized by ring-opening polymerization of lactide onto the hydroxyI groups of CDA.The resultant CDA-g-PLA copolymers possess adjustable degrees of substitution(DSpua)and side chain length(DPpLa)by controlling the reaction time and feed ratio.The Tgs and thermal flow temperatures(Ts)of CDA-g-PLA strongly depend on DPpA such as the Tgs decrease linearly with the increase of DPA.The CDA-g-PLA copolymers with the DPLA of 3-9 can be directly processed to transparent plastics by melt processing without any external plasticizers,because of their low Tfs of 170-215℃.More impressively.the CDA-g PLA can act as the macromolecular plasticizer.The obtained CDA/CDA-g-PLA has higher storage modulus,flexural modulus and Young's modulus than the commercial CDA plasticized with triethyl citrate.In addition,the CDA/CDA-g PLA exhibits high dimensional stabilty and anti-migration property.During a long term treatment at 80℃ and 60%humidity,the CDA/CDA-g-PLA can retain the initial shape.Therefore,this work not only proposes a facile method for achieving a direct thermoplastic processing of CDA,but also provides a macromolecular plasticizer for CDA to make lightweight,stable and safer biobased thermoplastics.
文摘In this work, controlling of the particle size of PVC in PS/PVC blends was studied. It is shown that viscosity ratio and particle size can be changed by adding a third composition, such as plasticizers, and the distribution of the third composition in two phases plays a very important role in controlling viscosity ratio and particle size. When DOP was used as the plasticizer of PVC in PS/PVC blends, the particle size of PVC could not be reduced due to the transference of DOP into PS phase. When polycaprolactone (PCL) was used as the plasticizer of PVC in the same blends, the particle size of PVC could be descreased obviously because PCL does not migrate to PS phase.
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.
