In this study,epoxidized soybean oil(ESO)and ricinoleic acid(RA)were used to synthesize polyol esters,designated ESO-RA(ER)resin.The esters were further crosslinked with 4,4-diphenylmethane diisocyanate(PMDI)to create...In this study,epoxidized soybean oil(ESO)and ricinoleic acid(RA)were used to synthesize polyol esters,designated ESO-RA(ER)resin.The esters were further crosslinked with 4,4-diphenylmethane diisocyanate(PMDI)to create a biodegradable flame-retardant thermoset foam,referred to as ESO-RA-PMDI(ERP)foam,using water as a foaming agent.Additionally,flame retardants such as triethyl phosphate(TEP)and expanded graphite(EG)have been combined for foam preparation without the need for catalysts or foaming agents.The study findings showed that the incorporation of TEP and EG diminished the pulverization ratio while augmenting the compressive strength and shore hardness.Furthermore,the ERP foam exhibited exceptional flame retardant characteristics,as evidenced by a reported limiting oxygen index(LOI)value of 30.6vol%.A peak heat release rate of 97.12 kW/m^(2)was reported during the fire test.Significantly,a low peak smoke production rate(pSPR)of 0.026m^(2)/s and a total smoke production(TSP)of 0.62 m^(2)were achieved.In addition,ERP foam exhibited exceptional ultraviolet(UV)resistance,thermal insulation,and biodegradability.After 60 days of exposure to Penicillium sp.,foam containing both TEP and EG exhibited a mass loss of 9.39%,indicating that the incorporation of flame retardants did not negatively impact its biodegradability.展开更多
A novel epoxidized soybean oil-toughened-phenolic resin(ESO-T-PR)has been synthesized by etheri- fication graft and multi-amine curing ESO.Fourier transform infrared spectroscopy(FTIR)was adopted to investi- gate its ...A novel epoxidized soybean oil-toughened-phenolic resin(ESO-T-PR)has been synthesized by etheri- fication graft and multi-amine curing ESO.Fourier transform infrared spectroscopy(FTIR)was adopted to investi- gate its molecular structure and scan electron microscope(SEM)was used to observe the micro morphology of its impact fracture surface.This ESO-T-PR was adopted as the matrix resin to prepare paper copper clad laminate (P-CCL)and the properties of resulting P-CCL are found superior to the related Chinese National Standard.The toughing mechanism was investigated by comparing the impact strength,solderleaching resistance,flexural strength, peeling strength and morphology of this ESO-T-PR with those of other two ESO modified phenolic resins.It is demonstrated that during the synthesizing process of ESO-T-PR,the phenol hydroxyl is etherified by ESO or ESO epoxy resin prepolymer(ESO chain extension polymer)and the long ESO epoxy resin chain segments enhance the crosslink density of ESO-T-PR and consequently improve the impact toughness and solderleaching resistance of P-CCL made of ESO-T-PR.The ESO-T-PR is a cheap matrix resin with excellent properties to make P-CCL(elec- tric guide board).展开更多
This study investigated that epoxidized soybean oil （ESO） was blended as plasticizer with poly （lactic acid） （PLA） and its effects on the melt rheological properties, such as melt flow index, apparent shear visc...This study investigated that epoxidized soybean oil （ESO） was blended as plasticizer with poly （lactic acid） （PLA） and its effects on the melt rheological properties, such as melt flow index, apparent shear viscosity, and melt strength of the blends. PLA was blended by the twin-screw plastic extruder at five mass fractions： 3%, 6%, 9%, 12%, and 15% （based on PLA mass）. Melt flow index （MFI） was examined with a melt flow indexer. The results indicate that the blends of PLA/ESO had higher MFI than pure PLA, except for MFI at 9% reaching to the lowest point, even lower than that of pure PLA. Melt rheological properties were studied by a capillary rheometer in a temperature range of 160-180℃. The blends exhibited shear-thinning behavior and the apparent shear viscosity was well described by the power law in this shear rate region. The melt strength of PLA plasticized with 6% ESO reached the maximums. ESO was more effective in increasing the melt strength at the mass fractions less than 6%, which could toughen the blends to some extent. Therefore, the authors suggested the optimum addition level of 6%-9% ESO will get good melt rheological performance balance.展开更多
A novel kind of fully bio-based PSAs we re obtained through the curing reaction between two components derived from the plant oils:carboxyl-terminated polyricinoleate(PRA) fro m the castor oil and epoxidized soybean o...A novel kind of fully bio-based PSAs we re obtained through the curing reaction between two components derived from the plant oils:carboxyl-terminated polyricinoleate(PRA) fro m the castor oil and epoxidized soybean oil(ESO).The get content,glass transition temperature(Tg),rheological behavior,tensile strength,creep resistance and 180° peel strength of the PSAs were feasibly tailored by adjusting the component ratio of ESO to PRA.At low cross-linking level,the PSAs behaved like a viscous liquid and did not possess enough cohesiveness to sustain the mechanical stress during peeling,The PSAs cross-linked at or near the optimal stoichiometric conditions displayed an adhesive(interfacial) failure between the substrate and the adhesive layer,which were associated with the lowest adhesion levels.The PSAs with the dosage amount of ESO ranging from 10.20 wt% were tacky and flexible,which exhibited 1800 peel strength ranging from 0.4~2.3 N/cm;and could be easily removed without any residues on the adherend.The process for the preparation of the fully bio-based PSAs was environmentally friendly without using any orga nic solve nt or other toxic chemical,herein showing the great potential as sustainable materials.展开更多
The novel epoxidized soybean oil-modified-phenolic resin/clay nanocomposites(ESO-M-PR/CN)was prepared.The coupling agent-benzyldimethylphenylammonium chloride[C6H5CH2N^+(CH3)2C6H5Cl^-,B2MP]was adopted to modify the in...The novel epoxidized soybean oil-modified-phenolic resin/clay nanocomposites(ESO-M-PR/CN)was prepared.The coupling agent-benzyldimethylphenylammonium chloride[C6H5CH2N^+(CH3)2C6H5Cl^-,B2MP]was adopted to modify the interface between the organic and inorganic phases.The effect of the nanocomposite structure on its physical and chemical properties was discussed.During the synthesizing process of ESO-M-PR/CN,the phenol hydroxyl was etherified by ESO or ESO epoxy resin prepolymer to provide long ESO epoxy segments.Long ESO epoxy resin chain segments enhanced the crosslink density of ESO-M-PR/CN.The thermal and mechanical properties exhibit a significant improvement.The temperature at which a weight loss of 5%occurs increases from 287.1℃to 402.3℃.The flexural strength increases by 25%,while the flexural modulus increases by 39%.Moreover,the properties of resin were enhanced by the effect of the inorganic nanoparticles,while the size of the nanomontmorillonites in the phenolic resin was characterized with a scanning electron microscope.The particle size of inorganic montmorillonites in the modified system is less than 100 nm.展开更多
A novel phosphorous-containing acrylated epoxidized soybean oil-based(P-AESO)resin was developed via the ring-opening reaction of epoxidized soybean oil(ESO)with diphenylphosphinic chloride(DPPC),followed by acrylatio...A novel phosphorous-containing acrylated epoxidized soybean oil-based(P-AESO)resin was developed via the ring-opening reaction of epoxidized soybean oil(ESO)with diphenylphosphinic chloride(DPPC),followed by acrylation of the resulting groups.The chemical structure was characterized by Fourier transform infrared spectroscopy(FT-IR),and ^(1)H nuclear magnetic resonance(^(1)H NMR).Subsequently,the viscosity and volumetric shrinkage of the obtained P-AESO resins were studied.Then the oligomer was formulated into UV-curable coatings,and the mechanical,thermal,and coating properties of the resulting UV-cured bioresins were studied by tensile testing,dynamic mechanical thermal analysis(DMA),thermogravimetric analysis(TGA)coupled with FT-IR spectroscopy(TGA-FT-IR),hardness,adhesion,pencil hardness and chemical resistance.Furthermore,the UV-curing behavior of the P-AESO resin was determined by real-time realtime infrared(RT-IR).Meanwhile,compared with coating from acrylated epoxidized soybean oil(AESO),the P-AESO system coatings showed better volumetric shrinkage,excellent adhesion,and enhanced thermal and glass transition temperature(Tg)while maintaining reasonably final C=C conversions and cross-link density.For instance,the obtained P-AESO/trimethylolpropanetriacrylate(TMPTA)20 material possessed a volumetric shrinkage of 4.1%,Tg of 115.6℃,char yield of 9.47%,and final C=C conversions of 81.4%respectively,which exhibited superior values than that of the AESO/TMPTA20 material.The improvement of the P-AESO coating performances could contribute to the architectures that combined the structural features of phosphorous-containing rigid benzene.The developed P-AESO resin is promising for applications in the UV-curable coatings.展开更多
Resin plugging agents play a pivotal role in addressing casing damage in oil and gas fields.However,the widespread use of epoxy resin is constrained by its high cost and non-renewable origin,while plant-based resins o...Resin plugging agents play a pivotal role in addressing casing damage in oil and gas fields.However,the widespread use of epoxy resin is constrained by its high cost and non-renewable origin,while plant-based resins often suffer from inadequate mechanical properties,which limit their effectiveness in such applications.This study introduces BEOPA,an innovative,renewable,high-strength resin plugging agent derived from epoxidized soybean oil(ESO)and enhanced with bisphenol A-type benzoxazine(BZ).In this study,the synthesis process,reactionmechanism,and application performance of this novelmaterial are systematically presented,explored and optimized.It is shown that the optimal formulation of BEOPA includes 41.4 wt%ESO,24.8 wt%BZ,24.8 wt%methylhexahydrophthalic anhydride(MHHPA),8.2 wt%styrene(ST),and 0.8 wt%N,N-dimethylbenzylamine(BDMA),yielding an impressive compressive strength of 93.7 MPa.The integration of ESO and BZ creates an intricate and robust double crosslinking network,significantly enhancing material strength and durability.BEOPA exhibits a tunable curing time,ranging from 0.5 to 15 h,with viscosities below 300 mPa⋅s at 25℃and 75mPa⋅s at 50℃.Furthermore,it demonstrates exceptional thermal stability within the 100℃-150℃range,even in environments with mineral salt concentrations as high as 43,330 mg/L.Remarkably,BEOPA achieves superior plugging performance,sustaining breakthrough pressures exceeding 29.7 MPa in 1 mm crack cores.展开更多
Currently adopted cross-linking methods in rubber industry are suffering from variable persistent issues, including the utilization of toxic curing packages, release of volatile organic compounds (VOCs) and difficulti...Currently adopted cross-linking methods in rubber industry are suffering from variable persistent issues, including the utilization of toxic curing packages, release of volatile organic compounds (VOCs) and difficulties in the recycling of end-of-life materials. It is of great importance to explore a green cross-linking strategy in the area. Herein, we report a new ‘‘green" strategy based on hydrolyzable ester cross-links for cross-linking diene-typed elastomers. As a proof of concept, a commercial carboxylated nitrile rubber (XNBR) is efficiently cross-linked by a bio-based agent, epoxidized soybean oil (ESO), without any toxic additives. ESO exhibits an excellent plasticization effect and excellent scorch safety for XNBR. The crosslinking density and mechanical properties of the ESO-cured XNBR can be manipulated in a wide range by changing simply varying the content of ESO. In addition, zinc oxide (Zn O) performs as a catalyst to accelerate the epoxide opening reaction and improve the cross-linking efficiency, serving as reinforcement points to enhance the overall mechanical properties of the ESO-cured XNBR. Furthermore, the end-oflife elastomer materials demonstrate a closed-loop recovery by selectively cleaving the ester bonds, resulting in very high recovery of the mechanical performance of the recycled composites. This strategy provides an unprecedented green avenue to cross-link diene elastomers and a cost-effective approach to further recycle the obtained cross-linked elastomers at high efficiency.展开更多
基金financially supported by the National Natural Science Foundation of China(No.32460363)Yunnan Province Agricultural Joint Key Foundation(No.202401BD070001-029)+3 种基金as well as the Yunnan Provincial Youth top talent project(No.YNWR-QNBJ-2020-166)Foreign Expert Workstation(No.202305 AF150006)111 project(No.D21027)Yunnan Province Natural Science Key Foundation(No.202301AS070043)。
文摘In this study,epoxidized soybean oil(ESO)and ricinoleic acid(RA)were used to synthesize polyol esters,designated ESO-RA(ER)resin.The esters were further crosslinked with 4,4-diphenylmethane diisocyanate(PMDI)to create a biodegradable flame-retardant thermoset foam,referred to as ESO-RA-PMDI(ERP)foam,using water as a foaming agent.Additionally,flame retardants such as triethyl phosphate(TEP)and expanded graphite(EG)have been combined for foam preparation without the need for catalysts or foaming agents.The study findings showed that the incorporation of TEP and EG diminished the pulverization ratio while augmenting the compressive strength and shore hardness.Furthermore,the ERP foam exhibited exceptional flame retardant characteristics,as evidenced by a reported limiting oxygen index(LOI)value of 30.6vol%.A peak heat release rate of 97.12 kW/m^(2)was reported during the fire test.Significantly,a low peak smoke production rate(pSPR)of 0.026m^(2)/s and a total smoke production(TSP)of 0.62 m^(2)were achieved.In addition,ERP foam exhibited exceptional ultraviolet(UV)resistance,thermal insulation,and biodegradability.After 60 days of exposure to Penicillium sp.,foam containing both TEP and EG exhibited a mass loss of 9.39%,indicating that the incorporation of flame retardants did not negatively impact its biodegradability.
基金Supported by the Key Science&Technology Item of Guangdong Province(TC05B372-6).
文摘A novel epoxidized soybean oil-toughened-phenolic resin(ESO-T-PR)has been synthesized by etheri- fication graft and multi-amine curing ESO.Fourier transform infrared spectroscopy(FTIR)was adopted to investi- gate its molecular structure and scan electron microscope(SEM)was used to observe the micro morphology of its impact fracture surface.This ESO-T-PR was adopted as the matrix resin to prepare paper copper clad laminate (P-CCL)and the properties of resulting P-CCL are found superior to the related Chinese National Standard.The toughing mechanism was investigated by comparing the impact strength,solderleaching resistance,flexural strength, peeling strength and morphology of this ESO-T-PR with those of other two ESO modified phenolic resins.It is demonstrated that during the synthesizing process of ESO-T-PR,the phenol hydroxyl is etherified by ESO or ESO epoxy resin prepolymer(ESO chain extension polymer)and the long ESO epoxy resin chain segments enhance the crosslink density of ESO-T-PR and consequently improve the impact toughness and solderleaching resistance of P-CCL made of ESO-T-PR.The ESO-T-PR is a cheap matrix resin with excellent properties to make P-CCL(elec- tric guide board).
基金Supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (20030561014)
文摘This study investigated that epoxidized soybean oil （ESO） was blended as plasticizer with poly （lactic acid） （PLA） and its effects on the melt rheological properties, such as melt flow index, apparent shear viscosity, and melt strength of the blends. PLA was blended by the twin-screw plastic extruder at five mass fractions： 3%, 6%, 9%, 12%, and 15% （based on PLA mass）. Melt flow index （MFI） was examined with a melt flow indexer. The results indicate that the blends of PLA/ESO had higher MFI than pure PLA, except for MFI at 9% reaching to the lowest point, even lower than that of pure PLA. Melt rheological properties were studied by a capillary rheometer in a temperature range of 160-180℃. The blends exhibited shear-thinning behavior and the apparent shear viscosity was well described by the power law in this shear rate region. The melt strength of PLA plasticized with 6% ESO reached the maximums. ESO was more effective in increasing the melt strength at the mass fractions less than 6%, which could toughen the blends to some extent. Therefore, the authors suggested the optimum addition level of 6%-9% ESO will get good melt rheological performance balance.
基金Financial supports by the National Natural Science Foundation of China (Nos.51761135132 and 51822304) are sincerely acknowledged。
文摘A novel kind of fully bio-based PSAs we re obtained through the curing reaction between two components derived from the plant oils:carboxyl-terminated polyricinoleate(PRA) fro m the castor oil and epoxidized soybean oil(ESO).The get content,glass transition temperature(Tg),rheological behavior,tensile strength,creep resistance and 180° peel strength of the PSAs were feasibly tailored by adjusting the component ratio of ESO to PRA.At low cross-linking level,the PSAs behaved like a viscous liquid and did not possess enough cohesiveness to sustain the mechanical stress during peeling,The PSAs cross-linked at or near the optimal stoichiometric conditions displayed an adhesive(interfacial) failure between the substrate and the adhesive layer,which were associated with the lowest adhesion levels.The PSAs with the dosage amount of ESO ranging from 10.20 wt% were tacky and flexible,which exhibited 1800 peel strength ranging from 0.4~2.3 N/cm;and could be easily removed without any residues on the adherend.The process for the preparation of the fully bio-based PSAs was environmentally friendly without using any orga nic solve nt or other toxic chemical,herein showing the great potential as sustainable materials.
基金the Key Science&Technology Item of Guangdong province(No.TC05B372-6)
文摘The novel epoxidized soybean oil-modified-phenolic resin/clay nanocomposites(ESO-M-PR/CN)was prepared.The coupling agent-benzyldimethylphenylammonium chloride[C6H5CH2N^+(CH3)2C6H5Cl^-,B2MP]was adopted to modify the interface between the organic and inorganic phases.The effect of the nanocomposite structure on its physical and chemical properties was discussed.During the synthesizing process of ESO-M-PR/CN,the phenol hydroxyl was etherified by ESO or ESO epoxy resin prepolymer to provide long ESO epoxy segments.Long ESO epoxy resin chain segments enhanced the crosslink density of ESO-M-PR/CN.The thermal and mechanical properties exhibit a significant improvement.The temperature at which a weight loss of 5%occurs increases from 287.1℃to 402.3℃.The flexural strength increases by 25%,while the flexural modulus increases by 39%.Moreover,the properties of resin were enhanced by the effect of the inorganic nanoparticles,while the size of the nanomontmorillonites in the phenolic resin was characterized with a scanning electron microscope.The particle size of inorganic montmorillonites in the modified system is less than 100 nm.
基金Fundamental Research Funds of CAF(No.CAFYBB2017QA017)Natural Science Foundation of Jiangsu Province(No.BK20161122)。
文摘A novel phosphorous-containing acrylated epoxidized soybean oil-based(P-AESO)resin was developed via the ring-opening reaction of epoxidized soybean oil(ESO)with diphenylphosphinic chloride(DPPC),followed by acrylation of the resulting groups.The chemical structure was characterized by Fourier transform infrared spectroscopy(FT-IR),and ^(1)H nuclear magnetic resonance(^(1)H NMR).Subsequently,the viscosity and volumetric shrinkage of the obtained P-AESO resins were studied.Then the oligomer was formulated into UV-curable coatings,and the mechanical,thermal,and coating properties of the resulting UV-cured bioresins were studied by tensile testing,dynamic mechanical thermal analysis(DMA),thermogravimetric analysis(TGA)coupled with FT-IR spectroscopy(TGA-FT-IR),hardness,adhesion,pencil hardness and chemical resistance.Furthermore,the UV-curing behavior of the P-AESO resin was determined by real-time realtime infrared(RT-IR).Meanwhile,compared with coating from acrylated epoxidized soybean oil(AESO),the P-AESO system coatings showed better volumetric shrinkage,excellent adhesion,and enhanced thermal and glass transition temperature(Tg)while maintaining reasonably final C=C conversions and cross-link density.For instance,the obtained P-AESO/trimethylolpropanetriacrylate(TMPTA)20 material possessed a volumetric shrinkage of 4.1%,Tg of 115.6℃,char yield of 9.47%,and final C=C conversions of 81.4%respectively,which exhibited superior values than that of the AESO/TMPTA20 material.The improvement of the P-AESO coating performances could contribute to the architectures that combined the structural features of phosphorous-containing rigid benzene.The developed P-AESO resin is promising for applications in the UV-curable coatings.
基金supported by the National Natural Science Foundation of China(U23B20156,52174033).
文摘Resin plugging agents play a pivotal role in addressing casing damage in oil and gas fields.However,the widespread use of epoxy resin is constrained by its high cost and non-renewable origin,while plant-based resins often suffer from inadequate mechanical properties,which limit their effectiveness in such applications.This study introduces BEOPA,an innovative,renewable,high-strength resin plugging agent derived from epoxidized soybean oil(ESO)and enhanced with bisphenol A-type benzoxazine(BZ).In this study,the synthesis process,reactionmechanism,and application performance of this novelmaterial are systematically presented,explored and optimized.It is shown that the optimal formulation of BEOPA includes 41.4 wt%ESO,24.8 wt%BZ,24.8 wt%methylhexahydrophthalic anhydride(MHHPA),8.2 wt%styrene(ST),and 0.8 wt%N,N-dimethylbenzylamine(BDMA),yielding an impressive compressive strength of 93.7 MPa.The integration of ESO and BZ creates an intricate and robust double crosslinking network,significantly enhancing material strength and durability.BEOPA exhibits a tunable curing time,ranging from 0.5 to 15 h,with viscosities below 300 mPa⋅s at 25℃and 75mPa⋅s at 50℃.Furthermore,it demonstrates exceptional thermal stability within the 100℃-150℃range,even in environments with mineral salt concentrations as high as 43,330 mg/L.Remarkably,BEOPA achieves superior plugging performance,sustaining breakthrough pressures exceeding 29.7 MPa in 1 mm crack cores.
基金This work was supported by the National Natural Science Foundation of China(NSFC,51790501 and 51825303),the Basic Science Center Program of NSFC(51988102)the National Key Research and Development Program of China(2017YFB0306900 and 2017YFB0306904)the Beijing Advanced Innovation Center for Soft Matter Science and Engineering
文摘Currently adopted cross-linking methods in rubber industry are suffering from variable persistent issues, including the utilization of toxic curing packages, release of volatile organic compounds (VOCs) and difficulties in the recycling of end-of-life materials. It is of great importance to explore a green cross-linking strategy in the area. Herein, we report a new ‘‘green" strategy based on hydrolyzable ester cross-links for cross-linking diene-typed elastomers. As a proof of concept, a commercial carboxylated nitrile rubber (XNBR) is efficiently cross-linked by a bio-based agent, epoxidized soybean oil (ESO), without any toxic additives. ESO exhibits an excellent plasticization effect and excellent scorch safety for XNBR. The crosslinking density and mechanical properties of the ESO-cured XNBR can be manipulated in a wide range by changing simply varying the content of ESO. In addition, zinc oxide (Zn O) performs as a catalyst to accelerate the epoxide opening reaction and improve the cross-linking efficiency, serving as reinforcement points to enhance the overall mechanical properties of the ESO-cured XNBR. Furthermore, the end-oflife elastomer materials demonstrate a closed-loop recovery by selectively cleaving the ester bonds, resulting in very high recovery of the mechanical performance of the recycled composites. This strategy provides an unprecedented green avenue to cross-link diene elastomers and a cost-effective approach to further recycle the obtained cross-linked elastomers at high efficiency.
