1_3_二甲基_2_咪唑啉酮的合成和应用_张正

(10)申请公布号 CN 102093296 A(43)申请公布日 2011.06.15C N 102093296 A*CN102093296A*(21)申请号 201010565233.8(22)申请日 2010.11.30C07D 233/14(2006.01)B01F 17/32(2006.01)B01F 17/38(2006.01)(71)申请人广州星业科技股份有限公司地址510000 广东省广州市萝岗区经济技术开发区(72)发明人王振雨 孟巨光(74)专利代理机构广州知友专利商标代理有限公司 44104代理人周克佑(54)发明名称咪唑啉化合物的合成方法(57)摘要本发明公开了一种咪唑啉化合物的合成方法，以脂肪酸和羟乙基乙二胺为原料，在催化剂作用下和氮气气氛中，加热到80℃～150℃后开始梯度升温至190-220℃进行氮酰化反应，形成烷基酰胺，将形成的烷基酰胺进行梯度减压脱水成环，制备得咪唑啉化合物。

该合成方法工艺简单，对生产设备要求不高；采用本发明方法可以大幅度减少副产物双酰胺的生成量，制备的咪唑啉化合物中双酰胺的含量可以降低至0.5％(质量百分含量)以下；同时制备的咪唑啉化合物质量稳定，可以长时间放置而不出现浑浊现象。

(51)Int.Cl.(19)中华人民共和国国家知识产权局(12)发明专利申请权利要求书 1 页 说明书 3 页1.一种咪唑啉化合物的合成方法，其特征是：以脂肪酸和羟乙基乙二胺为原料，在催化剂作用下和氮气气氛中，加热到80℃～150℃后开始梯度升温至190～220℃进行氮酰化反应，形成烷基酰胺，将形成的烷基酰胺进行梯度减压脱水成环，制备得咪唑啉化合物。

2.根据权利要求1所述的咪唑啉化合物的合成方法，其特征是：所述的脂肪酸为饱和脂肪酸、不饱和脂肪酸、多不饱和脂肪酸、天然脂肪酸、合成脂肪酸、直链脂肪酸、异构脂肪酸和羟基脂肪酸中的一种或几种。

3.根据权利要求2所述的咪唑啉化合物的合成方法，其特征是：所述的饱和脂肪酸为辛酸、癸酸、月桂酸、十四酸、十六酸和硬脂酸中的一种或几种；所述的不饱和脂肪酸为油酸；所述的多不饱和脂肪酸为亚油酸；所述的天然脂肪酸为棕榈酸、棕榈仁油酸和椰子油酸中的一种或几种；所述的直链脂肪酸为辛酸、癸酸、月桂酸、十四酸、十六酸和硬脂酸中的一种或几种；所述的羟基脂肪酸为蓖麻油酸。

Trans.Nonferrous Met.Soc.China31(2021)832−841Physicochemical properties of1,3-dimethyl-2-imidazolinone−ZnCl2solvated ionic liquid and its application in zinc electrodepositionAi-min LIU1,Meng-xia GUO1,Zhong-ning SHI2,Yu-bao LIU3,Feng-guo LIU1,Xian-wei HU1,You-jian YANG1,Wen-ju TAO1,Zhao-wen WANG11.Key Laboratory for Ecological Metallurgy of Multimetallic Mineral(Ministry of Education),Northeastern University,Shenyang110819,China;2.State Key Laboratory of Rolling and Automation,Northeastern University,Shenyang110819,China;3.State Key Laboratory of Baiyunobo Rare Earth Resource Researches and Comprehensive Utilization,Baotou Research Institute of Rare Earths,Baotou014030,ChinaReceived12April2020;accepted10November2020Abstract:Zinc chloride(ZnCl2)was dissolved in the1,3-dimethyl-2-imidazolinone(DMI)solvent,and the metallic zinc coatings were obtained by electrodeposition in room-temperature ambient air.The conductivity(σ),viscosity(η), and density(ρ)of the DMI−ZnCl2solvated ionic liquid at various temperatures(T)were measured and fitted. Furthermore,cyclic voltammetry was used to study the electrochemical behavior of Zn(II)in the DMI−ZnCl2solvated ionic liquid,indicating that the reduction of Zn(II)on the tungsten electrode was a one-step two-electron transfer irreversible process.XRD and SEM−EDS analysis of the cathode product confirmed that the deposited coating was metallic zinc.Finally,the effects of deposition potential,temperature and duration on the morphology of zinc coatings were investigated.The results showed that a dense and uniform zinc coating was obtained by potentiostatic electro-deposition at−2V(vs Pt)and353K for1h.Key words:electrodeposition;zinc;1,3-dimethyl-2-imidazolinone;physicochemical properties;cyclic voltammetry1IntroductionZinc is usually deposited on the surface of steel materials to obtain a dense and uniform coating with excellent adhesion.Zinc,used as a sacrificial anode,can protect the steel materials against corrosion[1].Conditional production of zinc coatings was carried out with electrodeposition in the aqueous cyanide,basic non-cyanide,and chloride solutions.However,the electrodeposition of zinc in aqueous solutions has disadvantages such as hydrogen embrittlement,wastewater treatment, and low current efficiency[2,3].Thus,it is of significant direction to seek new solvents from which high-quality zinc coatings can be deposited without environmental pollution.In recent years,the electrodeposition of zinc and its alloys in ionic liquids have attracted increasing attention from pared with aqueous solutions,ionic liquids have better thermal stability,lower vapor pressure,and wider electrochemical windows[4−6].LIN and SUN[7] reported that zinc could be electrodeposited from the ZnCl2−1-methyl-3-ethylimidazolium chloride (ZnCl2−MEIC with molar ratio of1:1)and ZnCl2−AlCl3−MEIC ionic liquid at potential of −0.8V(vs Al).HSIU et al[8]investigated the influence of electrolyte composition on the electrochemical window of the ZnCl2−1-ethyl-3-methylimidazolium chloride(ZnCl2−EMIC)ionic liquid,indicating that the electrochemical windowCorresponding author:Zhong-ning SHI;Tel:+86-24-83686381;E-mail:************** DOI:10.1016/S1003-6326(21)65542-51003-6326/©2021The Nonferrous Metals Society of China.Published by Elsevier Ltd&Science PressAi-min LIU,et al/Trans.Nonferrous Met.Soc.China31(2021)832−841833was−2V when the ZnCl2−EMIC ionic liquid was acidic,and zinc coating was able to deposit at −0.05V(vs Zn)and383K.DENG et al[9] electrodeposited zinc in the N-butyl-N-methyl-pyrrolidinium dicyandiamide(BMP-DCA)ionic liquid containing ZnCl2at−2.4V(vs Fc/Fc+)and 323K.Zn and Zn−Au alloy were obtained on a Au electrode by electrodeposition in the ZnCl2−1-butyl-3-methylimidazolium chloride(ZnCl2−BMIC with molar ratio of3:2)ionic liquid,while Zn−Co alloy was produced from the ZnCl2−BMIC ionic liquid containing1.16wt.%CoCl2[10,11]. However,above ionic liquids are expensive,and electrodeposition experiments should be performed in a glove box filled with inert gas because these ionic liquids are sensitive to the air and water, which greatly limits their industrial application.Deep eutectic solvents(DES),which were first described by ABBOTT in2003,have been widely studied for electrochemical application due to their low cost.XU et al[12]obtained Zn−Ti alloy by electrodeposition in the ZnCl2−urea(molar ratio of 3:1)DES containing0.27mol/L TiCl4at353K. YANG et al[13]prepared Zn−Ni alloy coating from the choline chloride−urea(ChCl−urea with molar ratio of1:2)DES containing0.1mol/L NiCl2 and0.4mol/L ZnCl2at343K,while CHU et al[14] prepared Zn−Co alloy coating from the DES containing0.11mol/L ZnCl2and0.01mol/L CoCl2. LI et al[15]added0.10g/L GO(graphene oxide)to the ChCl−urea DES containing0.2mol/L ZnCl2, and successfully produced a novel Zn−GO composite coating by pulse electrodeposition. SANCHEZ et al[16]prepared Zn−Ce coating in the ChCl-urea DES containing0.3mol/L ZnCl2and 0.1mol/L CeCl3.LI et al[17]electrodeposited Zn−Ni alloy coatings with controllable components and excellent corrosion resistance by adding5wt.% water to the ChCl−urea DES containing0.08mol/L NiCl2and0.4mol/L ZnCl2.BAO et al[18] explored the electrochemical deposition of Zn from lactate−ChCl(molar ratio of2:1)at a constant current density of10mA/cm2.BAKKAR and NEUBERT[19]obtained bulk Zn layers from the ChCl−urea−EG(ethylene glycol)DES(molar ratio of1:1.5:0.5)at potential ranging from−1.2to −1.5V(vs Ag).VIEIRA et al[20]investigated the electrochemical behavior of zinc in the ChCl−EG (molar ratio of1:2)DES containing ZnCl2on different electrodes including glassy carbon,stainless steel,Au,Pt,Cu and Zn.PEREIRA et al[21]prepared zinc from the ChCl−EG DES containing5×10−4mol/mL ZnCl2,and found that the additive of dimethyl sulfoxide(DMSO)could achieve grain refinement and produce zinc with a minimum grain size of31.7nm.ALESARY et al[22]obtained a bright zinc coating by adding nicotinic acid,boric acid,and benzoquinone to the ChCl−EG DES containing6×10−4mol/mL ZnCl2.ENDO et al[23]found that a smooth aluminium film can be obtained by electrode-position in the1,3-dimethyl-2-imidazolidinone−AlCl3(DMI−AlCl3)ionic liquid at313K when the content of AlCl3was higher than50at.%.Recently, ZHANG et al[24]reported an exceptional organic solvent composed of DMI and LiNO3,and directly deposited a La film from LaCl3at−2.3V(vs Ag) and298K.It was found that the DMI solvent has good solubility and coordination ability for chlorides,and it has advantages including low cost, low melting point,being insensitive to water,and wide electrochemical window.In this work,ZnCl2 was dissolved in the DMI solvent for zinc electrodeposition.The conductivity,viscosity and density of the DMI−ZnCl2solvated ionic liquid at different temperatures were measured.Furthermore, the solubilities of ZnCl2in the DMI solvent at different temperatures were measured,and the electrochemical behavior of Zn(II)in DMI−ZnCl2 ionic liquid was investigated by cyclic voltammetry and potentiostatic electrodeposition.2ExperimentalZinc chloride(ZnCl2,98%)and1,3-dimethyl-2-imidazolidinone(DMI,99%)were purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd.,China.The DMI−ZnCl2solvated ionic liquid was prepared by adding0.29g/mL ZnCl2to the DMI solvent and stirring on a magnetic heating plate in ambient atmosphere.The conductivity, viscosity,and density of the ionic liquid were measured based on the fixed cell constant method, the rotation method,and the Archimede’s principle, respectively.Moreover,the solubilities of ZnCl2in the DMI solvent were measured by the equilibrium method.Cyclic voltammetry was performed using a three-electrode system by a electrochemical workstation(CHI600E,Shanghai ChenhuaAi-min LIU,et al/Trans.Nonferrous Met.Soc.China31(2021)832−841 834Instrument,Shanghai,China).A tungsten wire (99.99%,diameter of1mm)was used as the working electrode,while two platinum wires (99.99%,diameter of1mm)were used as the counter electrode and the reference electrode, respectively.The surface of electrodes were polished with sandpapers,cleaned with ethanol and deionized water,and then dried before the measurement of cyclic voltammogram.The working electrode was immersed in the ionic liquid with depth of1.4cm.Electrodeposition experiments were also carried out using a three-electrode system by the CHI600E electrochemical workstation.The working electrode was a tungsten sheet(99.99%, side area of1cm2),while the counter electrode and the reference electrode were platinum wires.After electrodeposition experiments,the surface of the working electrode was washed with acetone and distilled water,dried naturally and then stored in a glove box,in which the contents of water and oxygen were below1×10−6.X-ray diffraction(XRD, D8ADVANCE,Bruker,Germany)was used to analyze the phase structure of the zinc deposited on tungsten substrates.In addition,the surface morphology and elemental composition of zinc coatings were studied by a scanning electron microscope(SEM,ULTRA PLUS,Zeiss Microscope,Germany)combined with X-ray dispersive energy spectrometer(EDS).3Results and discussion3.1Physical and chemical properties of DMI−ZnCl2solvated ionic liquidThe relationship between the conductivities of the DMI−ZnCl2solvated ionic liquid and temperature(313−303K)is shown in Fig.1(a).It can be seen that the conductivity increased from 0.571to0.932mS/cm when the temperature increased from313to363K.This was because the increase of the temperature was beneficial to the diffusion of ions in the ionic liquid,which promoted the mass transfer rate and caused the increased of conductivity.However,the increase rate of conductivity was small at353−363K.Fig.1Conductivities of DMI−ZnCl2solvated ionic liquid as function of temperature(a),relationship between lnσand T−1(b),viscosities of DMI−ZnCl2solvated ionic liquid as function of temperature(c)and relationship between lnηand T−1(d)Ai-min LIU,et al/Trans.Nonferrous Met.Soc.China31(2021)832−841835The conductivity of the DMI−ZnCl2solvated ionic liquid was of the same order of magnitude as that of some conventional ionic liquids ranging from0.1to10mS/cm[25].For example,the conductivity of the EMIC ionic liquid at298K was reported to be 3.43−3.71mS/cm[26].In comparison,the conductivity of the DMI−ZnCl2 solvated ionic liquid was much smaller than that of the aqueous solution containing3.7mol/L ZnCl2at 298K(107mS/cm)[27].However,the conductivity of the DMI−ZnCl2solvated ionic liquid was larger than that of the urea−ZnCl2(molar ratio of3:1) DES at298K(0.051mS/cm)[12],and the urea−ZnCl2(molar ratio of3.5:1)and ChCl−ZnCl2 (molar ratio of1:2)DES at315K(0.18and 0.06mS/cm,respectively)[28].As we know,the DMI solvent is an organic liquid with small conductivity.Therefore,it can be indicated that the conductivity of the DMI solvent was modified by the Lewis acidic cation Zn(II),and the DMI−ZnCl2 solvated ionic liquid that has similar characteristics as conventional ionic liquid was obtained.In general,the relationship between the conductivity of ionic liquid and temperature can be expressed using the Arrehnius equation[25]:lnσ=lnσ0−Eσ/(RT)(1) whereσis the conductivity(mS/cm),σ0is a pre-factor(mS/cm),Eσis the conductivity activation energy(kJ/mol),R is the ideal gas constant(8.314J·K−1·mol−1),and T is the temperature(K).As shown in Fig.1(b),there was a good linear relationship between lnσand T−1. Through linear fitting,the relationship between the conductivity of DMI−ZnCl2solvated ionic liquid and temperature can be expressed by Eq.(2),and the activation energy of the conductivity was determined to be9.387kJ/mol:lnσ=3.095−1129.059/T(2) The high viscosity of ionic liquids is one of the bottlenecks preventing them from gaining large-scale industrial applications.In general,the viscosity of ionic liquid is determined by the internal van der WAALS force and the interaction of hydrogen bonds.Thus,suitable additives are added to the ionic liquid to reduce the viscosity.In this work,the viscosities of the DMI−ZnCl2 solvated ionic liquid at323−373K were measured by the rotation method.The relationship between the viscosities of the DMI−ZnCl2solvated ionic liquid and temperature is shown in Fig.1(c).The viscosity decreased with increasing temperature because the van der WAALS force and hydrogen bond strength within the system changed with temperature.Furthermore,the relationship between viscosity and temperature can be expressed by the Arrhenius formula[29]:lnη=lnη0+Eη/(RT)(3) whereηis viscosity(mPa·s),η0is a pre-factor (mPa·s),and Eηis the activation energy of viscosity (kJ/mol).As shown in Fig.1(d),there was a good linear relationship between lnηand T−1.By linear fitting,the relationship between the viscosity of DMI−ZnCl2solvated ionic liquid and temperature can be expressed by Eq.(4),and the activation energy of the viscosity was determined to be 8.364kJ/mol:lnη=−0.033+1006.014/T(4) The densities of the DMI−ZnCl2solvated ionic liquid at313−373K were measured by the Archimede’s principle.The relationship between the densities of the DMI−ZnCl2solvated ionic liquid and temperature is shown in Fig.2.Fig.2Densities of DMI−ZnCl2solvated ionic liquid as function of temperatureIt can be found from Fig.2that the density demonstrated a linear relationship with temperature. Besides,the density gradually decreased from1.205 to1.163g/cm3with temperature increasing from 313to373K,and the trend was relatively flat.This is because when the temperature increased,the migration rate and spacing of particles in the ionic liquid increased,which caused the expansion of volume.Since the number of particles per unit area was diminished at higher temperature,the density became smaller.Through linear fitting,the densitiesAi-min LIU,et al/Trans.Nonferrous Met.Soc.China31(2021)832−841 836of the DMI−ZnCl2solvated ionic liquid at differenttemperatures can be expressed using the followingequation:ρ=−6.464×10−4T+1.406(5)whereρis the density(g/cm3).The concentration of ZnCl2in the DMI−ZnCl2solvated ionic liquid is an important parameterduring the process of zinc electrodeposition.Hence,the effect of temperature on the solubilities of ZnCl2in the DMI solvent was explored.The solubilitiesof ZnCl2in the DMI solvent at313,333,353and373K were determined to be0.29,0.32,0.45,and 1.58g/mL,respectively.With temperatureincreasing from313to353K,the solubility ofZnCl2gradually increased from0.29to0.45g/mL.It was worth noting that when the temperatureincreased from353to373K,the solubilities ofZnCl2significantly increased from0.45to1.58g/mL.However,the ionic liquid at373Kbecame very viscous,and eventually turnedinto a transparent colloid which was no longersuitable for zinc electrodeposition.Therefore,it wasnot recommended to perform zinc electro-deposition experiments with saturated ZnCl2concentration,especially at temperature higher than 373K.Therefore,the measurement of physico-chemical properties and electrochemical experiments in this work were carried out in the DMI−ZnCl2 solvated ionic liquid containing0.29g/mL ZnCl2at 313−373K.3.2Electrochemical behavior of Zn(II)in DMI−ZnCl2solvated ionic liquidThe electrochemical behavior of Zn(II)ions in the DMI−ZnCl2solvated ionic liquid at313K was studied by cyclic voltammetry using a tungsten working electrode.It can be seen from Fig.3(a)that the cyclic voltammetry curve from1to−3V(vs Pt) was a straight line,and the current was almost zero, indicating that the DMI solvent was stable within this potential range.When0.29g/mL ZnCl2was dissolved in the DMI solvent,a pair of redox peaks were found within the electrochemical window of the DMI solvent.Obviously,the reduction peak corresponds to the reduction of Zn(II)ions to metallic zinc,while the oxidation peak was related to the peeling of metal zinc from the electrode surface.The onset potential of the reduction of Zn(II)ions was−1.13V(vs Pt),and the potential of the oxidation peak was−0.13V(vs Pt).Fig.3Cyclic voltammetry curves on tungsten electrode in DMI solvent and DMI−ZnCl2solvated ionic liquid at 313K(scan rate of40mV/s)(a)and in DMI−ZnCl2 solvated ionic liquid at353K and different scan rates(b) As seen in Fig.3(b),the current densities ofthe oxidation peaks increased as the scan rate increased from20to100mV/s,and the potential of the oxidation peaks shifted to the more positive values.However,the scan rate had no obvious influence on the current density and potential of the reduction peak,indicating that the reduction reaction was not controlled by diffusion.Besides, only one reduction signal was observed.Therefore, the reduction of Zn(II)was a one-step two-electron transfer irreversible reaction process.Moreover,it should be noted that a“nucleation loop”related to the nucleation of the deposited zinc was observed.3.3Effect of deposition potential,temperatureand duration on zinc coatingsThe process of metal electrodeposition includes the formation and growth of crystal nuclei, and overpotential is the driving force for nucleation. According to the analysis from the cyclicAi-min LIU,et al/Trans.Nonferrous Met.Soc.China 31(2021)832−841837voltammetry curve,different potentials were applied to the electrodeposition experiments performed at 353K for 1h.The XRD patterns of the cathode products obtained by deposition at potentials of −1.4,−1.6,−1.8and −2V (vs Pt)are shown in Fig.4(a).The characteristic peaks at 2θ=57.9°and 72.8°were corresponding to the tungsten substrate,while the other diffraction peaks in the XRD patterns matched well with the characteristic peaks of zinc (ICDD 00-004-0836),which confirmed that the cathode product was metallic zinc [30].As the applied potential shifted from −1.4V to more negative potential of −2V ,the intensity of the XRD diffraction peak for zinc became greater,indicating that the zinc coating deposited on the surface of tungsten substrate at −2V was thicker.Moreover,the preferred orientations for zinc crystal growth were the (002)and (101)planes.Fig.4XRD patterns of zinc coatings obtained by electrodeposition on tungsten electrode in DMI−ZnCl 2solvated ionic liquid for 1h:(a)At 353K and different potentials (from −1.4to −2V (vs Pt));(b)At −2V (vs Pt)and different temperatures (from 313to 373K)The effect of temperature on the zinc coating was studied by electrodeposition experiments performed at −2V (vs Pt)for 1h.The XRD patterns of the cathode products obtained by electrodeposition at temperatures of 313,333,353and 373K are shown in Fig.4(b).When the temperature increased from 313to 353K,the intensity of the XRD diffraction peak for zinc increased.However,when the electrodeposition temperature increased from 353to 373K,the intensity of the XRD diffraction peak for zinc did not continue to increase.Based on the analysis from XRD patterns,it could be concluded that a better zinc coating was obtained by electrodeposition at −2V (vs Pt)and 353K.As shown in the inset of Fig.5(a),a dark gray coating was obtained on the surface of the tungsten substrate by electrodepositing in the DMI−ZnCl 2solvated ionic liquid at −2V (vs Pt)and 353K.The SEM image (Fig.5(a))showed that the coating obtained by potentiostatic electrodeposition at −2V (vs Pt)and 353K was dense and uniform,whichFig.5SEM image (a)and EDS spectrum (b)of zinc coating obtained by electrodeposition on tungsten electrode in DMI−ZnCl 2solvated ionic liquid at −2V (vs Pt)and 353K for 1hAi-min LIU,et al/Trans.Nonferrous Met.Soc.China 31(2021)832−841838was in accordance with the results from XRD analysis.In addition,the EDS spectrum of the coating demonstrated that the elemental compositions of the coating were 99.51wt.%Zn and 0.49wt.%Cl.The small amount of Cl element came from the ionic liquid containing ZnCl 2.The SEM images of the cathode coatings obtained by potentiostatic electrodeposition at different potentials (vs Pt)and temperatures are shown in Figs.6and 7,respectively.From Fig.6,Fig.6SEM images of zinc coatings obtained by electrodeposition on tungsten electrodes in DMI−ZnCl 2solvated ionic liquid at 353K and various potentials (vs Pt)for 1h:(a)−1.4V;(b)−1.6V;(c)−1.8V;(d)−2VFig.7SEM images of zinc coatings obtained by electrodeposition on tungsten electrodes in DMI−ZnCl 2solvated ionic liquid at −2V (vs Pt)and different temperatures for 1h:(a)313K;(b)333K;(c)353K;(d)373KAi-min LIU,et al/Trans.Nonferrous Met.Soc.China31(2021)832−841839 when the potential changed from−1.4to−2V(vsPt),the grain size of the deposited metal zincbecame smaller because the nucleation density andnucleation rate increased as the applied potentialshifted to the more negative values.Moreover,thecrystal morphology changed from irregular tohexagonal particles,and a uniform zinc coating wasobtained by electrodeposition at−2V(vs Pt).LINand SUN[7]proposed similar results about theinfluence of potential on the micro-morphology ofzinc coating deposited from the AlCl3−MEIC−ZnCl2ionic liquid.From Fig.7,as the temperature increased from313to373K,the grain size of the deposited metalzinc became larger.It could be explained that withthe increase of temperature,the driving force of ionmigration and the growth of metal core wereaccelerated,which resulted in the increase of grainsize.XU et al[12]reported similar results about theinfluence of temperature on the micro-morphologyof Zn−Ti alloy prepared by electrodeposition in theurea−ZnCl2deep eutectic solvent.Figure8(a)exhibits the XRD patterns of zinccoatings obtained by electrodeposition on tungsten electrodes at−2V(vs Pt)and353K for different durations.The characteristic peaks of metallic zinc were observed on all of the XRD patterns.When the deposition time was0.5h,the characteristic peaks of the tungsten substrate were obvious.As the deposition time was extended,the intensity of the zinc characteristic peaks increased due to the changes of the thickness of zinc coatings,which was further confirmed by the cross-sectional SEM images as demonstrated in Fig.8(b).When the deposition time increased from0.5to2h,the thickness of zinc coatings increased approximately from6.7to32μm.4Conclusions(1)The conductivities of the DMI−ZnCl2 solvated ionic liquid at313−363K were in the range of0.571−0.932mS/cm,which can be expressed by lnσ=3.095−1129.059/T.(2)The viscosities and densities of the DMI−ZnCl2solvated ionic liquid were in the range of22.20−14.70mPa·s(323−373K)and1.205−1.163g/cm3(313−373K),which can be expressed by lnη=−0.033+1006.014/T andρ=−6.464×10−4T+ 1.406,respectively.Fig.8XRD patterns(a)and SEM images(b)for cross section of zinc coatings obtained by electrodeposition on tungsten electrodes in DMI−ZnCl2solvated ionic liquid at−2V(vs Pt)and353K for different durations(3)The solubilities of ZnCl2in the DMI solvent at313K was0.29g/mL,and ZnCl2was used as precursor to electrodeposite zinc coatings in the DMI−ZnCl2solvated ionic liquid at room temperature and ambient air.(4)Results from cyclic voltammetry showed that the onset reduction potential of zinc was −1.13V(vs Pt).XRD and SEM−EDS analysis confirmed that metallic zinc was obtained by electrodeposition for1h,while the preferred deposition potential and temperature were−2V(vs Pt)and353K.AcknowledgmentsThe authors are grateful for the financial supports from the Fundamental Research Funds for the Central Universities,China(N182503033, N172502003),Postdoctoral Research Foundation of China(2018M640258),the National Natural Science Foundation of China(51804070)and Guangxi Innovation-driven Development Program, China(GUIKE AA18118030).Ai-min LIU,et al/Trans.Nonferrous Met.Soc.China31(2021)832−841 840References[1]KRISHNAN R M,NATARAJAN S R,MURALIDHARANV S,SINGH G.Characteristics of a non-cyanide alkaline zinc plating bath[J].Plating and Surface Finishing,1992,79: 67−70.[2]RAMESH BAPU G N K,DEVARAJ G,AYYAPPARAJ J.Studies on non-cyanide alkaline zinc electrolytes[J].Journal of Solid State Electrochemistry,1998,3:48−51.[3]LIU Z,ZEIN El ABEDIN S,ENDRES F.Electrodepositionof zinc films from ionic liquids and ionic 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(10)申请公布号(43)申请公布日 (21)申请号 201410774016.8(22)申请日 2014.12.16C23F 11/02(2006.01)(71)申请人中国石油天然气股份有限公司地址100007 北京市东城区东直门北大街9号中国石油大厦(72)发明人刘帮华 解永刚 田喜军 韩东兴樊志强 王轩 王蕾 王霞胡均志 黄雪萍 常霞 马鹏飞刘建生(74)专利代理机构西安吉盛专利代理有限责任公司 61108代理人张培勋(54)发明名称一种咪唑啉类缓蚀剂、合成方法及其应用(57)摘要本发明涉及一种咪唑啉类缓蚀剂、合成方法及其应用，适用于天然气处理厂锅炉的防腐工作，其主剂为松香，助剂为二乙烯三胺和N，N 一二甲基乙酰胺，另外，在合成咪唑啉类缓蚀剂的基础上，引入带有在CO2／N2作用下具有“开一关”性能的脒基，一方面提高咪唑啉类缓蚀剂对CO2的缓蚀性能；另一方面使得缓蚀剂能够循环再次利用。

最后，在模拟现场条件下，发现缓蚀剂加量400mg/L 时，缓蚀率达80%，腐蚀速率缓蚀效率良好；该缓蚀剂以抑制阴极析氢还原反应为主，也有阳极金属溶解作用，属于阴极抑制型为主的混合控制型缓蚀剂。

本发明所涉及的缓蚀剂成本低廉，使用方式简单、高效、低毒、无刺激气味并且减少了对于水体与环境的污染。

(51)Int.Cl.(19)中华人民共和国国家知识产权局(12)发明专利申请权利要求书2页 说明书7页 附图3页(10)申请公布号CN 104513991 A (43)申请公布日2015.04.15C N 104513991A1. 一种咪唑啉类缓蚀剂，其特征在于：该咪唑啉类缓蚀剂是由松香与二乙烯三胺反应得到咪唑啉中间体，然后再与N,N-二甲基乙酰胺反应得到松香-咪唑啉-N，N-二甲基乙脒，最后再与二氧化碳反应所得到。

2.一种如权利要求1所述的咪唑啉类缓蚀剂的合成方法，包括如下步骤：步骤一：将松香与二乙烯三胺反应得到咪唑啉中间体，化学反应式如下，步骤二：将步骤一所得到的咪唑啉中间体与N,N-二甲基乙酰胺反应得到松香-咪唑啉-N，N-二甲基乙脒没化学反应式如下，步骤三：将步骤二得到的松香-咪唑啉-N，N-二甲基乙脒与二氧化碳反应得到松香-咪唑啉-乙脒碳酸氢盐，化学反应式如下，。

1. 介绍1,3-二甲基-2-咪唑啉酮，又称为DMPK，是一种药物代谢动力学和药理学领域中常见的化合物。

该化合物在药物代谢过程中起着重要作用，因此对其水解过程进行深入的研究具有重要的意义。

2. 化合物结构1,3-二甲基-2-咪唑啉酮是一种含氮杂环化合物，其结构中包含两个甲基基团和一个咪唑啉酮环。

其化学结构如下所示：[C+2]-1,3-Dimethyl-1H-imidazol-2-yl-ketone3. 水解机制1,3-二甲基-2-咪唑啉酮在水解过程中通常经历以下几个步骤：A. 亲核加成：水分子中的氢离子攻击1,3-二甲基-2-咪唑啉酮中的羰基碳，形成一个亲核加成中间体。

B. 分解：亲核加成中间体进一步分解，产生主要的水解产物。

C. 形成产物：分解过程中生成的产物会随后脱离1,3-二甲基-2-咪唑啉酮分子。

4. 影响因素1,3-二甲基-2-咪唑啉酮水解过程受多种因素的影响，主要包括：A. pH值：水解反应通常在酸性或碱性条件下进行，pH值的变化会对水解速率产生影响。

B. 温度：温度的升高通常会加快水解反应的进行，但过高的温度也可能导致产物的降解。

C. 催化剂：某些特定的化合物或金属离子可能作为催化剂参与水解反应，加速反应速率。

5. 应用领域1,3-二甲基-2-咪唑啉酮水解的研究在药物代谢动力学、药理学和生物化学领域具有广泛的应用价值。

了解其水解机制能够帮助人们更好地理解药物在体内的代谢过程，为新药的研发和临床应用提供重要参考。

6. 研究进展近年来，关于1,3-二甲基-2-咪唑啉酮水解的研究逐渐增多。

基于该化合物的水解特性，科研人员不断探索更高效的水解方法，以及在药物代谢动力学和药理学领域中的具体应用。

7. 结论1,3-二甲基-2-咪唑啉酮水解作为一种重要的研究课题，对于推动药物代谢动力学和药理学领域的发展具有重要意义。

通过深入的研究和探索，相信在未来会有更多关于其水解机制和应用价值的突破性发现。

1,3-二甲基-2-咪唑啉酮的水解是一个值得深入探讨的领域，其水解过程对于药物代谢动力学和药理学领域有着重要的意义。

(19)中华人民共和国国家知识产权局(12)发明专利申请(10)申请公布号 (43)申请公布日 (21)申请号 201911178343.6(22)申请日 2019.11.27(71)申请人 济宁康盛彩虹生物科技有限公司地址 272300 山东省济宁市鱼台县张黄镇工业园区富康大道北首路东(72)发明人 钱继东　黄定乾　盛蕊　闫伟伟　(74)专利代理机构 北京中济纬天专利代理有限公司 11429代理人 宋震(51)Int.Cl.C07D 233/52(2006.01)B01J 31/02(2006.01)C07C 17/12(2006.01)C07C 25/00(2006.01)(54)发明名称一种N-双（二甲胺基）-1,3-二甲基咪唑啉制备方法及用途(57)摘要本发明涉及化合物制备方法及用途领域，尤其是一种N -双（二甲胺基）-1,3-二甲基咪唑啉制备方法及用途，化学分子式为：C 9H 23N 5；制备方法包括如下步骤：S1：以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉；这既解决了其他氯代试剂的安全、环保问题，也极大的提高了产品收率（87%以上）。

S2：向上述生成的氯盐中滴加四甲基胍，进行缩合反应；S3：再对上述产物进行中和反应，得N -双（二甲胺基）亚甲基-1，3-二甲基-2-氯咪唑啉氯化铵盐。

本工艺可操作性强，反应条件温和，除生成高含量的氯化钾作为副产物外，几乎没有其他杂质生成，安全、绿色环保，产品催化效果好、适用范围广。

权利要求书1页 说明书3页CN 110845414 A 2020.02.28C N 110845414A1.一种N -双（二甲胺基）-1,3-二甲基咪唑啉，其特征在于：其化学分子式为：C 9H 23N 5；化学分子结构为：2.一种N -双（二甲胺基）-1,3-二甲基咪唑啉的制备方法，其特征在于：包括如下步骤：S1：以1,3-二甲基-2-咪唑啉、双(三氯甲基)碳酸酯为原料，进行氯代反应合成氯代1,3-二甲基-2-氯咪唑啉；这既解决了其他氯代试剂的安全、环保问题，也极大的提高了产品收率（87%以上）。

第61卷 第12期 化 工 学 报Vo l 61 No 122010年12月 CIESC Jo ur nal December 2010研究论文新型卡宾前体1,3 二取代 2 羧基咪唑(啉)的合成及表征王燕芹,李振江(南京工业大学生物与制药工程学院,材料化学工程国家重点实验室,江苏南京210009)摘要:性质稳定的1,3 二取代 2 羧基咪唑(啉)(N HC-CO 2)是一类重要的卡宾前体,以3条路线合成了一系列含有不同取代基结构的N HC CO 2。

通过核磁共振(1H NM R)、元素分析以及红外光谱(IR )对产物进行了结构表征。

利用热重/微商热重分析(T G /DT G )对产物的热脱羧性能进行了研究。

结果表明:随着温度升高,NH C CO 22 位羧基脱除,得到游离卡宾;芳基取代的N H C CO 2在50~350 间有脱羧和降解两个阶段,并且拥有相同芳香取代基的2 羧基咪唑和2 羧基咪唑啉具有相似的脱羧性能;烷基取代的N H C CO 2较芳香基取代的N HC CO 2初始脱羧温度低,且不存在降解阶段。

关键词:2 羧基咪唑(啉);卡宾;前体;脱羧中图分类号:O 626 23 文献标识码:A文章编号:0438-1157(2010)12-3117-07Synthesis and characterization of 1,3 disubstitutedimidazol (in)ium 2 carboxylatesWANG Yanqin,LI Zhenjiang(S tate K ey L abor ator y of M ater ials O riented Chemical Engineer ing ,Colleg e o f Biotechnology and Phar maceuticalEngineering,N anj ing Univer sity of T echnology ,N anj ing 210009,J iangsu,China )Abstract :The air and w ater stable 1,3 disubstituted imidazol (in)ium 2 car box y lates (NH C CO 2)as impo rtant precurso rs of N hetero cyclic carbenes w ere pr epared by three ro utes Nine kinds of NH C CO 2w ith different gr oups on nitrog en atoms w er e o btained The structure w as characterized by 1H NM R,elemental analy sis and IR Thermog ravimetric analy sis (TG/DTG )provided the evidence fo r decarbox ylatio n in NH C CO 2 T he results show that CO 2escapes from the m olecule in the process of elevating temperature and free carbenes are released T w o pro cesses (decarbox ylatio n and decom po sitio n)occur w hen the substituents on the nitrog en atoms are aryl gro up,and the imidazo lium 2 carbox ylates and the im idazolinium 2 carboxy lates show similar perform ance of decarboxy lation T he initial temperatures of mass loss are lower when the substituents on the nitrogen atoms are alkyl group,and no decomposition occurs Key words:imidazol (in)ium 2 carboxy lates;carbene;precursor;decarboxy lation2010-02-23收到初稿,2010-04-12收到修改稿。