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Unleashing the Power of bio-based Thermotropic Liquid Crystal Modifiers:Toughening and Reinforcing Petroleum-based Epoxy Resin without Compromising Other Properties

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Chinese Journal of Polymer Science 2024年第8期42卷 1093-1102页

作者： Qing-Yun Lu Hong-Wei Gu Jia-Hui Li Qian-Qian Fan Bei-Tao Liu Yan Kou Xi-Gao Jian Zhi-Huan Weng State Key Laboratory of Fine Chemicals Frontiers Science Center for Smart MaterialsLiaoning Technology Innovation Center of High Performance Resin MaterialsDepartment of Polymer Science&EngineeringDalian University of TechnologyDalian 116024China Thermochemistry Laboratory Liaoning Province Key Laboratory of Thermochemistry for Energy and MaterialsDalian National Laboratory for Clean EnergyDalian Institute of Chemical PhysicsChinese Academy of SciencesDalian 116023China

Toughening the petroleum-based epoxy resin blends with bio-based modifiers without compromising their modulus,mechanical strength,and other properties is still a big challenge in view of the *** this study,a bio-based liquid crystal epoxy resin(THMT-E P)with an s-triazine ring structure was utilized to modify a petroleum-based bisphenol A epoxy resin(E51)with 4,4'-diaminodiphenylsulfone(DDS)as a curing agent,and the blended systems were evaluated for their thermal stability,mechanical properties,and flame *** results showed that the impact strength of the blended system initially increased and then decreased with the increase in THMT-EP content,and it reached the a maximum value of 26.5 kJ/m^(2)when the THMT-EP content was 5%,which was 31.2%higher than that of E51/***,the flexural strength,modulus,and glass transition tem perature of the blended system were all simultaneously improved with the addition of *** the same time,the addition of THMT-EP enhanced the flame retardancy of the system by increasing the char yield at 700℃and decreasing the peak heat release rate and total heat release *** work paves the way for a more sustainable improvement in the comprehensive performance of epoxy resin.

关键词： Epoxy resin Toughening bio-based Thermotropic liquid crystal

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CO_(2)-Responsive Smart Foams Stabilized by an Extremely Rigid bio-based Surfactant

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Journal of Renewable Materials 2023年第2期11卷 523-538页

作者： Weishan Tang Xin Feng Caiyun Lin Xiaoping Rao College of Chemical Engineering Huaqiao UniversityXiamen361021China

Environment friendly and intelligent surfactants have attracted great attention in recent years.A bio-based CO_(2)responsive surfactant rosin acid dimaleimide choline(R-BMI-C)with an extremely rigid skeleton was prepared using rosin and choline as raw materials by Diels-Alder addition reaction and acid-base neutralization *** structure was confirmed by IR and^(1)H NMR *** foams’properties of R-BMI-C could be adjusted by bubbling CO_(2)/N_(2)to change the structure of the *** pH 10.4,R-BMI-C forms an unstable foam with a half-life of 1.5 *** the pH was reduced to 7.4 by bubbling CO_(2),R-BMI-C forms an extremely stable foam with a half-life of 336 *** surfactant R-BMI-C changed from bola type to conventional type when bubbling CO_(2).And the internal aggregation structure of R-BMI-C aqueous solution changed from spherical micelles to laminar micelles according to the cryogenic-transmission electron *** know that the lamellar structure tends to adsorb at the air/water interface or is trapped in the foam film,which slows down the foam coarsening and agglomeration process,resulting in a significant increase in foam stability.R-BMI-C could be used in oil extraction,fire-fighting and chemical decontamination due to its excellent foaming,stabilization and defoaming properties.

关键词： Rosin bio-based surfactant CO_(2)-responsive foams

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Curing kinetics and mechanical properties of bio-based composite using rosin-sourced anhydrides as curing agent for hot-melt prepreg

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Science China(Technological Sciences) 2017年第9期60卷 1318-1331页

作者： ZHANG XuFeng WU YunQiQiGe WEI JiaHu TONG JianFeng YI XiaoSu Beijing Institute of Aeronautical Materials Beijing 100095 China Aviation Composite Corparation (Beijing) Science and Technology Co. Ltd Beijing 101300 China

In this study, a novel bio-based thermosetting system has been developed from epoxy resin （EP）, with rosin-sourced anhydrides （maleopimaric acid, RAM） as curing agent and imidazole type latent catalyst （two amino imidazole salt complex, IMA）, to be used as matrix for hot-melt prepreg curing at mid-temperature. For comparison, the epoxy resin system with petroleum sourced hardener methylhexahydrophthalicanhydride （MHHPA） was also examined. The curing behaviour and mechanism were investigated by non-isothermal differential scanning calorimeter （DSC） analysis and Fourier transform infrared （FTIR） spectra. The results showed that the curing course of bio-based epoxy resin system containing RAM included two stages, which were the reaction between the free carboxyl group of RAM and oxirane ring under the acceleration of IMA, and the main reaction attributed to the reaction between anhydride and oxirane. According to Kissinger method, the reaction activation energy （E,） of two stages were 68.9 and 86.5kJmo1-1, respectively. The Eo of EP/MHHPA and EP/IMA resin system were 81.04 and 77.9kJmol-I. The processing property of EP/RAM/IMA system, i.e. the relationship between viscosity-temperature-time, was characterized by cone-plate viscometer aim to decide the processing parameter ofprepreg preparation. The effect of RAM content on mechanical performance and dynamic mechanical property was investigated. Noteworthily, compared with the laminates with EP/MHHPA as matrix, the laminates with RAM as hardeners achieved a 44%, 73% and 70℃ increase in bending strength, bending modulus and the glass transition temperature, respectively, due to the bulky hydrogenated phenanthrene ring structure incorporated into the cross-linking networks. When the fiber volume fraction reached 47%, the mechanical property of the laminates prepared with hot melt prepreg was superior or comparable to that of composites with pure petroleum sourced matrix. RAM as cross-linking agent of epoxy resin holds a g

关键词： bio-based epoxy resin rosin cure kinetics hot-melt prepreg mechanical property

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Synthesis and properties of phosphorus-containing bio-based epoxy resin from itaconic acid

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Science China Chemistry 2014年第3期57卷 379-388页

作者： MA SongQi LIU XiaoQing JIANG YanHua FAN LiBo FENG JianXiang ZHU Jin Ningbo Key Laboratory of Polymer Materials Ningbo Institute of Material Technology and Engineering Chinese Academy of Sciences

A phosphorus-containing bio-based epoxy resin(EADI)was synthesized from itaconic acid(IA)and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide(DOPO).As a matrix,its cured epoxy network with methyl hexahydrophthalic anhydride(MHHPA)as the curing agent showed comparable glass-transition temperature and mechanical properties to diglycidyl ether in a bisphenol A(DGEBA)system as well as good flame retardancy with UL94 V-0 grade during a vertical burning *** a reactive flame retardant,its flame-resistant effect on DGEBA/MHHPA system as well as its influence on the curing behavior and the thermal and mechanical properties of the modified epoxy resin were *** showed that after the introduction of EADI,not only were the flame retardancy determined by vertical burning test,LOI measurement,and thermogravimetric analysis significantly improved,but also the curing reactivity,glass transition temperature(T g),initial degradation temperature for 5%weight loss(T d(5%)),and flexural modulus of the cured system improved as *** has great potential to be used as a green flame retardant in epoxy resin systems.

关键词： epoxy resin bio-based itaconic acid DOPO flame retardancy

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Synthesis of Eugenol bio-based Reactive Epoxy Diluent and Study on the Curing Kinetics and Properties of the Epoxy Resin System

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Chinese Journal of Polymer Science 2019年第5期37卷 500-508页

作者： Bin Chen Feng Wang Jing-Yu Li Jia-Lu Zhang Yan Zhang Hai-Chao Zhao School of Materials Science and Engineering Shenyang University of Chemical Technology Key Laboratory of Marine Materials and Related Technologies Zhejiang Key Laboratory of Marine Materials and Protective TechnologiesNingbo Institute of Materials Technology and EngineeringChinese Academy of Sciences

In this study, monoglycidyl silyl etherated eugenol(GSE) was synthesized as reactive epoxy diluent, and the chemical structure of GSE, intermediates, and products were characterized by Fourier transform infrared spectroscopy(FTIR) and nuclear magnetic resonance(~1 H-NMR). GSE existed as a potential bio-based reactive diluent for petroleum-based epoxy resin. The curing kinetics of EP/HHPA/GSE system was studied by non-isothermal DSC method. The kinetics parameters were calculated by using the Kissinger model, Crane model, Ozawa model, and β-T(temperature-heating rate) extrapolation, respectively. In addition, the effects of GSE on the thermo-mechanical properties and thermal stability of EP/HHPA/GSE systems were studied, indicating that GSE can effectively improve the toughness and thermal decomposition temperature of the epoxy system.

关键词： bio-based epoxy Reactive diluent Eugenol Curing kinetics

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The Spatial and Electronic Effects of Substituent Groups on the Thermal Curing of bio-based Benzoxazines

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Journal of Renewable Materials 2021年第12期9卷 2093-2117页

作者： Rumeng Li Guozhu Zhan Qi Ma Yunhe Yang Xiaoyun Liu Yitong Zhang Qixin Zhuang Laboratory of Specially Functional Polymeric Materials and Related Technology(ECUST) Ministry of EducationEast China University of Science and TechnologyShanghai200237China The 806th Institute of the Eighth Academy of CASC Huzhou313000China

To explore the influence of substituent groups on thermally induced curing,eight new bio-based benzoxazines containing different substituent groups with different electron negativity and volumes were *** thermal curing of these bio-based benzoxazines was studied in *** with the curing reaction kinetics,simulation and calculation of Highest Occupied Molecular and Lowest Unoccupied Molecular values,the spatial and electronic effects of different substituent groups on the curing of benzoxazine was *** was found that when the substituent was located at the position directly connected to the N atom,the steric hindrance effect of the group was *** the substituent group was located on the benzene ring connected to the O atom,both the electronic effect and the spatial effect influenced the curing of *** an electron-withdrawing group was connected ortho position to the O atom,the curing reaction was promoted due to the decreased electron cloud density of O-on the oxazine ring,making the C-O bond easier to *** an electron-donating group was connected to the meta position of the O atom it also promoted the curing reaction,possibly because it increased the electron cloud density of the+CH2 reaction site and thereby facilitated electrophilic substitution via attack of+CH2 on the cross linking reaction *** work provides a deeper understanding of how spatial and electronic effects of substituents affect the curing of benzoxazine.

关键词： Benzoxazine spatial effects electronic effects bio-based

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A bio-based epoxy resin derived from p-hydroxycinnamic acid with high mechanical properties and flame retardancy

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Chinese Chemical Letters 2022年第11期33卷 4912-4917页

作者： Xin Song Ze-Peng Deng Chun-Bo Li Fei Song Xiu-Li Wang Li Chen De-Ming Guo Yu-Zhong Wang The Collaborative Innovation Center for Eco-Friendly and Fire-Safety Polymeric Materials(MoE) National Engineering Laboratory of Eco-Friendly Polymeric Materials(Sichuan)State Key Laboratory of Polymer Materials EngineeringCollege of ChemistrySichuan UniversityChengdu 610064China

Recent advances in epoxy resins have been forward to achieving high mechanical performance,thermal stability,and flame ***,seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing *** we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer(HCA-EP)via a simple one-step reaction,and the HCA-EP can be cured with 4,4′-diaminodiphenylmethane(DDM)to prepare epoxy *** with the typical petroleum-based epoxy resin,bisphenol A epoxy resin,the HCA-EP-DDM shows a relatively high glass transition temperature(192.9℃)and impressive mechanical properties(tensile strength of 98.3 MPa and flexural strength of 158.9 MPa).Furthermore,the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%.Notably,its char yield is as high as 31.6%under N_(2),and the peak heat rate release is 60%lower than that of bisphenol A epoxy *** findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.

关键词： Epoxy resin bio-based p-Hydroxycinnamic acid Mechanical performance Intrinsic flame retardancy

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Elastic bio-based Polyurethane Nanofibrous Membrane with Robust Waterproof and Breathable Properties

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Journal of Donghua University(English Edition) 2023年第3期40卷 237-246页

作者：刘浩克王婷闫子硕斯阳俞建勇丁彬 College of Materials Science and Engineering Donghua UniversityShanghai 201620China Innovation Center for Textile Science and Technology Donghua UniversityShanghai 200051China State Key Laboratory for Modification of Chemical Fibers and Polymer Materials Donghua UniversityShanghai 201620China

Elastic bio-based waterproof and breathable membranes(EBWBMs) allow the passage of water vapor effectively and resist the penetration of liquid water,making it ideal for use under extreme *** this study,we used a facile strategy to design the bio-based polyurethane(PU) nanofibrous membranes with the nanoscale porous structure to provide the membranes with high waterproof and breathable *** optimization of nanofibrous membrane formation was accomplished by controlling the relative ambient humidity to modulate the cooperating effects of charge dissipation and non-solvent-induced phase *** obtained EBWBMs showed multiple functional properties,with a hydrostatic pressure of 86.41 kPa and a water vapor transmission(WVT) rate of 10.1 kg·m^(-2)·d^(-1).After 1 000 cycles of stretching at 40% strain,the EBWBMs retained over 59% of the original maximum stress and exhibited an ideal elasticity recovery ratio of 85%.Besides,even after 80% deformation,the EBWBMs still maintained a hydrostatic pressure of 30.65 kPa and a WVT rate of 13.6 kg·m^(-2)·d^(-1),suggesting that bio-based PU nanofibrous membranes could be used for protection under extreme conditions.

关键词： bio-based polyurethane(PU) electrospinning waterproof breathable membrane

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Synthesis,Characterization and Water Absorption Analysis of Highly Hygroscopic bio-based Co-polyamides 56/66

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Journal of Donghua University(English Edition) 2023年第6期40卷 631-638页

作者：杜瑞满程刊刘涛乌彤秦鸿彬王学利潘星夷冯旭马博谋何勇 State Key Laboratory for Modification of Chemical Fibers and Polymer Materials College of Material Science and EngineeringDonghua UniversityShanghai 201620China Innovation Center for Textile Science and Technology Donghua UniversityShanghai 201620China The People’s Liberation Army Joint Logistic Support Force Quartermaster Energy Quality Supervision Station Beijing 100071China

This study aims to develop highly hygroscopic bio-based co-polyamides(CPs)by melt co-polycondensation of polyamide(PA)56 salt and PA66 salt with varying molar *** functional groups and the chemical structure of the prepared samples were determined by Fourier transform infrared(FTIR)spectroscopy and proton nuclear magnetic resonance(^(1)H-NMR)*** relative viscosity was determined with an Ubbelohde *** melting behavior and the thermal stability of CPs were investigated by differential scanning calorimetry(DSC)and thermogravimetric analysis(TGA).Furthermore,the water absorption behavior of CP hot-pressed film was *** results reveal that the melting point,the crystallization temperature and the crystallinity of CPs firstly decrease and then increase with the molar fraction of PA66 in *** copolymerization of PA56 with PA66 leads to an obvious increase in water *** CPs with PA66 molar fraction of 50%possess a high saturated water absorption rate of 17.6%,compared to 11.6%for pure PA56 and 7.8%for pure PA66.

关键词： bio-based PA56 hygroscopic co-polyamide(CP) melt polycondensation water absorption

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bio-based Polymers for Technical Applications: A Review — Part 2

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Open Journal of Polymer Chemistry 2014年第4期4卷 95-101页

作者： Kayode Feyisetan Adekunle Polymer Group School of Engineering University of Boras Boras Sweden Department of Chemical Engineering College of Engineering and Engineering Technology Michael Okpara University of Agriculture Umudike Nigeria

Triglyceride oil of plant seed cannot be used on its own without further modification. The fatty acids must be suitably functionalized in order to add polymerisable functionalities which will help in the curing process. The purpose of these modifications is to reach a higher level of molecular weight and cross-link density, and also to incorporate chemical functionalities known to impart stiffness in a polymer network. The modification can go through various path ways which were described in this study.

关键词： Plant Oils Thermoset Synthesis bio-based Curing

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