CN114057622A - 一种短链双咪唑季铵盐及其制备与检测方法 - Google Patents
一种短链双咪唑季铵盐及其制备与检测方法 Download PDFInfo
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- -1 bisimidazole quaternary ammonium salt Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000001514 detection method Methods 0.000 title abstract description 14
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000002835 absorbance Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical class C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
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- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 23
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 6
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 5
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- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 5
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical group 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
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- 238000005260 corrosion Methods 0.000 description 3
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
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- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
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- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
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- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000002390 rotary evaporation Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- GTQHJCOHNAFHRE-UHFFFAOYSA-N 1,10-dibromodecane Chemical compound BrCCCCCCCCCCBr GTQHJCOHNAFHRE-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical compound BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- GGQOPZKTDHXXON-UHFFFAOYSA-N hexane;methanol Chemical compound OC.CCCCCC GGQOPZKTDHXXON-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/323—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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Abstract
本发明公开了一种短链双咪唑季铵盐及其制备与检测方法。该制备方法包括以下步骤:二卤代烷和N‑甲基咪唑进行反应,反应结束后洗涤数次,干燥即得所述短链双咪唑季铵盐;所述二卤代烷的结构式为:X‑(CH2)n‑X,其中X为卤素,n为2‑12的整数。本发明以二卤代烷和N‑甲基咪唑为原料,采用一步法快速高效的合成了系列短链双咪唑季铵盐,其原料单一且利用率高、操作简单、反应温度低、时间短、无需复杂的纯化步骤,更有利于短链双咪唑季铵盐的工业化生产,以及作为驱油剂在油田开发中的应用。并且本发明所提供的短链双咪唑季铵盐的检测方法可以快速简便地检测水溶液中短链双咪唑季铵盐的浓度,如驱油后其在驱替液和采出液中的含量。
Description
技术领域
本发明涉及有机合成领域,具体涉及一种短链双咪唑季铵盐及其制备与检测方法。
背景技术
季铵盐是一种广泛使用的化工产品,其中,短链单、双和多季铵盐可作为分子沉积(MD)膜剂应用于油田开发领域(高芒来,于凯.单分子双季铵盐在油田驱油和原油破乳中的用途[P].北京:CN1227305 A,1999.高芒来.单分子单季铵盐和单分子多季铵盐的用途[P].北京:CN1510101 A,2002.高芒来.单分子季铵盐的催化裂化用途[P].北京:CN1509814 A,2002.高芒来.单分子季铵盐化合物作为粘土稳定、防膨和解堵增注剂的用途[P].北京:CN1556169 A,2004.)。通过与油藏表/界面的静电相互作用,短链季铵盐可以在油藏表面和内部形成就一层的纳米级分子沉积膜,从而提高采收率。此外,短链季铵盐还可作为粘土稳定、防膨和解堵增注剂,有效改善水油井增注效果。
双咪唑季铵盐是一种通过两个亲脂链和两个通过间隔基共价连接的极性咪唑鎓头基组成,因其特殊的结构,咪唑季铵盐具有良好的物理化学性质,如较低的临界胶束浓度、较高的生物活性、较低的毒性和刺激性、抗微生物活性、良好的缓蚀性和亲水亲油性等特性。因其结构和性质特点,双咪唑季铵盐可广泛应用在工业、化工、生物医药等领域。在表面活性剂领域,可作为阴离子增效剂、抗静电剂和杀菌剂;在石油化工领域,可作为增稠剂、驱油剂、压裂液、缓蚀剂、粘土防膨剂等;在水处理领域,可作为絮凝剂、破乳剂、吸附剂、改性剂等。
短链双咪唑盐分子结构中含有两个N+和两个带有短烷基链的不饱和咪唑环,既具有咪唑离子液体的性质,又有季铵盐的性质。相比于传统的短链季铵盐,短链双咪唑盐的化学活性更好,绿色环保性更强,可与带负电的油藏矿物表/界面相互作用,可以在较短时间和较低浓度下有效的在油藏矿物表/界面静电自组装成单层膜,调变油藏矿物润湿性,提高油藏采收率。
短链双咪唑季铵盐可作为一种新型驱油剂,原料廉价易得,使用浓度低,绿色环保,驱替过程损耗少,地质损害小,施工工艺简单,可以有效调节表面润湿性,提高原油采收率明显。而现有报道的短链双咪唑季铵盐的合成方法具有诸多不适宜工业化生产的缺陷,如合成时间长、原料利用率低、纯化步骤复杂等。
Zhang等(Hang Zhang,Mingtao Li,Bolun Yang.Design,synthesis,andanalysis of thermophysical properties for imidazolium-based geminaldicationic ionic liquids[J].J.Phys.Chem.C,2018(122):2467-2474.)用N-烷基咪唑和二溴乙(丁)烷以2:1.1的摩尔比加入圆底烧瓶,以乙醇为溶剂在70℃下在氮气保护下回流24h,用乙酸乙酯萃取反应物数次,其固体产物在真空烘箱干燥24h即得双咪唑季铵盐。该技术现有缺点有五:其一,该技术中的反应物比例中二溴烷烃的用量较多,易导致副产物1-乙基-3-烷基咪唑溴化物的生成;其二,该技术反应时间较长,不利于工业化生产;其三,由于该反应较为剧烈,反应过程会放出大量的热,该技术的反应温度较高,不利于反应的正向进行;其四,该技术需要在氮气保护下进行,增加了合成的条件限制、技术难度、操作难度和安全风险,不适宜工业化批量生产;其五,该技术仅提及并适用于N-烷基咪唑和二溴乙(丁)烷的合成,并不适用于其他二卤代短链双咪唑季铵盐的制备。
Baltazar等(Quinner Q.Baltazar,Janaki Chandawalla,Keahna Sawyer,JaredL.Anderson.Interfacial and micellar properties of imidazolium-basedmonocationic and dicationic ionic liquids[J].Colloid Surface A,2007(302):150-156.)用N-烷基咪唑和二溴乙(丁)烷以2:1的摩尔比加入圆底烧瓶,以异丙醇为溶剂在70℃下搅拌回流24h。反应结束后,减压蒸出异丙醇,将产物溶于去离子水中,并用乙酸乙酯萃取反应物5次,后80℃下真空除水,并在真空烘箱干燥2天后得到产物。该技术缺点有五:其一,该技术的反应物比例不能保证N-烷基咪唑充分过量,容易在合成过程中生成单溴代咪唑季铵盐副产物;其二,该技术的反应时间长,不利于工业化生产;其三,该技术的反应温度较高,不利于反应的正向进行;其四,该技术先将产物溶于去离子水后再进行萃取、除水、烘干等步骤进行纯化,合成步骤繁杂,不易操作,此外,由于产物易溶于水,处理后产物晶体中仍会存在大量的结晶水和吸附水,导致合成产物产率和产物纯度降低,不利于大批量的工业化生产;其五,该技术仅提及并适用于N-烷基咪唑和二溴乙(丁)烷的合成,并不适用于其他二卤代短链双咪唑季铵盐的制备。
观文娜等(观文娜,王诗雨,毛鑫涛.一种双阳离子型咪唑类离子液体及其制备方法[P].山东:CN110407754 A,2019.)以咪唑、二溴烷烃、长链卤代烷为原料,通过两步合成的方法合成一种双阳离子型咪唑类离子液体。首先,将咪唑与二溴代烷烃在60-70℃下反应48-72h,所得的产物经甲醇正己烷萃取后,旋蒸除溶剂后干燥过夜。其次,将上述产物与长链卤代烷在乙腈或二氧六环中加热反应48-72h,所得产物旋蒸、萃取并真空干燥,即得到目标产物。该技术缺点有三:其一,该合成技术为两步法合成,后续处理步骤繁琐;其二,该技术的所需原料和溶剂较多,增加了合成成本,不利于大规模的工业生产;其三,每一步的合成时间都需48h以上,合成的周期长。
针对短链双咪唑季铵盐驱油剂的以上优势以及现有合成方法不适合工业化的缺陷,本发明旨在以一步法简便和高产率的制备系列短链双咪唑季铵盐,并提供一种短链双咪唑季铵盐在水溶液中含量的快速准确的检测方法。
发明内容
本发明的目的在于提供一种短链双咪唑季铵盐及其制备方法,以推广短链双咪唑季铵盐的工业化生产及其在油田开发方面的应用。本发明制备方法的原料单一、反应时间短、产率高、操作简单。并且,为了快速简便监测驱油后短链双咪唑季铵盐在驱替液和采出液中的浓度,本发明提供了一种简便、快捷、准确、高效的短链双咪唑季铵盐的检测方法。
为了实现以上目的,本发明采用以下技术方案:
本发明一方面提供一种短链双咪唑季铵盐的制备方法,该制备方法包括以下步骤:
二卤代烷和N-甲基咪唑进行反应,反应结束冷却后产物析出,洗涤、干燥即得所述短链双咪唑季铵盐;
所述二卤代烷的结构式为:X-(CH2)n-X,其中X为卤素,n为2-12的整数。
本发明的短链双咪唑季铵盐的合成反应式如图1所示,其中,n=2-12,X=F、Cl、Br或I。
根据本发明的制备方法,优选地,所述二卤代烷和N-甲基咪唑的摩尔比为1:(2.05-2.5)。
为保证反应的产率,同时也减少副产物的生成,本发明的制备方法必须保证N-甲基咪唑过量,而现有的技术中的反应物比例均不能保证N-甲基咪唑的过量反应。经本发明研究,所述二卤代烷和N-甲基咪唑的摩尔比为1:(2.05-2.5)时,N-甲基咪唑适当过量,二者可进行充分反应,反应产率可达85%以上。
根据本发明的制备方法,优选地,所述反应的溶剂选自C2-C4的醇类、乙腈、丙酮、二氯甲烷、氯仿和乙酸乙酯中的一种或两种以上的组合。更优选地,所述反应的溶剂为乙醇、异丙醇或二者的混合溶剂。
根据本发明的制备方法,优选地,所述洗涤的洗涤溶剂选自乙酸乙酯、C1-C4的醇类、乙醚、丙酮和乙腈中的一种或两种以上的组合。更优选地,所述洗涤的洗涤溶剂为乙酸乙酯。
根据本发明的制备方法,优选地,所述反应的温度为55-65℃。
根据本发明的制备方法,优选地,所述反应的时间为6-18h。
本发明的制备方法相较于现有技术,采用更低的温度、更短的时间、更简便的操作制备了高产率高纯度的短链双咪唑季铵盐。
根据本发明的制备方法,优选地,所述干燥为真空干燥,温度为60-80℃。
本发明另一方面提供一种以上制备方法得到的短链双咪唑季铵盐。
本发明再一方面提供一种以上短链双咪唑季铵盐的检测方法,该检测方法包括以下步骤:
制备不同浓度的短链双咪唑盐标准水溶液;
用紫外-可见分光光度计测得短链双咪唑盐的紫外最大吸收波长,并在紫外最大吸收波长处测所述短链双咪唑盐标准溶液的吸光度;
绘制短链双咪唑盐的浓度-吸光度的标准曲线;
用紫外-可见分光光度计在短链双咪唑盐的紫外最大吸收波长处测得待测样的吸光度,所述待测样为含有短链双咪唑盐的溶液;通过测定的吸光度结合所述标准曲线计算得到待测样中短链双咪唑盐的浓度。
本发明基于短链双咪唑盐特殊的结构,在224±1nm左右有紫外最大吸收波长,因此可通过紫外-可见分光光度计快速精确检测其在水溶液中的含量。
本发明的制备方法以二卤代烷和N-甲基咪唑为原料,采用一步法快速高效的合成了系列短链双咪唑季铵盐,其原料单一且利用率高、操作简单、反应温度低、时间短、无需复杂的纯化步骤,更有利于短链双咪唑季铵盐的工业化生产,以及作为驱油剂在油田开发中的应用。并且本发明所提供的短链双咪唑季铵盐的检测方法可以快速简便地检测驱油后短链双咪唑季铵盐在驱替液和采出液中的浓度,待测样无需处理,可直接检测计算得到其中短链双咪唑盐的浓度。
附图说明
图1为本发明短链双咪唑盐的合成方程式。
图2为实施例1中所得1,2-双(3-甲基-1-咪唑盐基)溴代乙烷的浓度-吸光度的标准曲线图。
图3为实施例2中所得1,4-双(3-甲基-1-咪唑盐基)溴代丁烷的浓度-吸光度的标准曲线图。
图4为实施例3中所得1,6-双(3-甲基-1-咪唑盐基)溴代己烷的浓度-吸光度的标准曲线图。
图5为实施例4中所得1,10-双(3-甲基-1-咪唑盐基)溴代癸烷的浓度-吸光度的标准曲线图。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
本发明中的短链双咪唑盐指短链双咪唑季铵盐,其分子式为:MeMI+-(CH2)n-MeMI+2X-,其中,n=2-12。MeMI为N-甲基咪唑,X为F、Cl、Br、I等卤素原子。X-(CH2)n-X指的是二卤代烷烃,n=2-12,X=F、Cl、Br、I。EBMI指的是1,2-双(3-甲基-1-咪唑盐基)溴代乙烷。TBMI指的是1,4-双(3-甲基-1-咪唑盐基)溴代丁烷。HBMI指的是1,6-双(3-甲基-1-咪唑盐基)溴代己烷。DBMI指的是1,10-双(3-甲基-1-咪唑盐基)溴代癸烷。
本发明所有数值指定(例如温度、时间、浓度及重量等,包括其中每一者的范围)通常可是适当以0.1或1.0的增量改变(+)或(-)的近似值。所有数值指定均可理解为前面有术语“约”。
实施例1
本实施例制备了1,2-双(3-甲基-1-咪唑盐基)溴代乙烷(EBMI),并绘制了相应的浓度-吸光度的标准曲线。
将0.1mol的1,2-二溴乙烷与0.205mol的N-甲基咪唑加入到盛有乙醇/异丙醇溶剂的圆底烧瓶中,65℃下反应12h,反应结束冷却后有产物析出,用乙酸乙酯洗涤3次,并置于真空干燥箱中80℃烘干,即得固体产品1,2-双(3-甲基-1-咪唑盐基)溴代乙烷(EBMI),产率为85.1%。
1,2-双(3-甲基-1-咪唑盐基)溴代乙烷(EBMI):
1H-NMR(400MHz,D2O):δ8.93(s,2H),7.62(s,2H),7.53(s,2H),4.89(s,4H),4.01(s,6H);Elemental analysis,cal.(%):C,34.09;H,4.55;N,15.91,found(%):C,32.72;H,4.66;N,15.28。
配制浓度为0.0124mmol/L、0.0247mmol/L、0.0494mmol/L、0.0740mmol/L、0.0988mmol/L、0.124mmol/L、0.198mmol/L的7个EBMI标准水溶液,用紫外-可见分光光度计在224nm处测其吸光度,以吸光度为横坐标,浓度为纵坐标,绘制标准曲线。拟合曲线,所得的标准曲线如图2所示,得EBMI标准曲线方程:y=4.23192x+0.01629,y为EBMI溶液所测得的吸光度,x为EBMI溶液浓度,mmol/L。方程线性相关系数R2=0.9996,即准确率达到了99.96%,线性关系良好。
配置浓度为0.0594mmol/L的EBMI溶液,测其吸光度为0.268,经标准曲线计算得浓度为0.595mmol/L,实际浓度与计算浓度相差不大,说明该检测方法灵敏可行。
实施例2
本实施例制备了1,4-双(3-甲基-1-咪唑盐基)溴代丁烷(TBMI),并绘制了相应的浓度-吸光度的标准曲线。
将0.1mol的1,4-二溴丁烷与0.205mol的N-甲基咪唑加入到盛有乙醇的圆底烧瓶中,在65℃下反应12h,反应结束冷却后有产物析出,用乙酸乙酯洗涤3次,并置于真空干燥箱中80℃烘干,即得固体产品1,4-双(3-甲基-1-咪唑盐基)溴代丁烷(TBMI),产率为80.6%。
1,4-双(3-甲基-1-咪唑盐基)溴代丁烷(TBMI):
1H-NMR(400MHz,D2O):δ8.81(s,2H),7.55(s,2H),7.49(s,2H),4.31(t,4H),3.94(s,6H),1.97(m,4H);Elemental analysis,cal.(%):C,37.89;H,5.26;N,14.74,found(%):C,37.74;H,5.09;N,14.49。
配制浓度为0.0124mmol/L、0.0246mmol/L、0.0369mmol/L、0.0492mmol/L、0.0615mmol/L、0.0738mmol/L、0.0984mmol/L、0.123mmol/L的8个TBMI标准溶液,用紫外-可见分光光度计在224nm处测其吸光度,以吸光度为横坐标,浓度为纵坐标,绘制标准曲线。拟合曲线,所得的标准曲线如图3所示,得TBMI标准曲线方程:y=3.4627x–0.00251,y为TBMI溶液所测得的吸光度,x为TBMI溶液浓度,mmol/L。方程线性相关系数R2=0.9997,即准确率达到了99.97%,线性关系良好。
配置浓度为0.0376mmol/L的TBMI溶液,测其吸光度为0.128,经标准曲线计算得浓度为0.0377mmol/L,实际浓度与计算浓度相差不大,说明该检测方法灵敏可行。
实施例3
本实施例制备了1,6-双(3-甲基-1-咪唑盐基)溴代己烷(HBMI),并绘制了相应的浓度-吸光度的标准曲线。
将0.1mol的1,6-二溴己烷与0.205mol的N-甲基咪唑加入到盛有乙醇的圆底烧瓶中,在65℃下反应12h,反应结束冷却后有产物析出,用乙酸乙酯洗涤3次,并置于真空干燥箱中80℃烘干,即得固体产品1,6-双(3-甲基-1-咪唑盐基)溴代己烷(HBMI),产率为83.5%。
1,6-双(3-甲基-1-咪唑盐基)溴代己烷(HBMI):
1H-NMR(400MHz,D2O):δ8.72(s,2H),7.47(s,2H),7.43(s,2H),4.19(t,4H),3.88(s,6H),1.88(m,4H),1.34(m,4H);Elemental analysis,cal.(%):C,41.16;H,5.88;N,13.72,found(%):C,41.15;H,5.88;N,13.49。
配制浓度为0.0124mmol/L、0.0246mmol/L、0.0369mmol/L、0.0492mmol/L、0.0615mmol/L、0.0738mmol/L、0.0984mmol/L、0.123mmol/L、0.197mmol/L的9个HBMI标准溶液,用紫外-可见分光光度计在224nm处测其吸光度,以吸光度为横坐标,浓度为纵坐标,绘制标准曲线。拟合曲线,所得的标准曲线如图4所示,得HBMI标准曲线方程:y=3.40544x+0.00947,y为HBMI溶液所测得的吸光度,x为HBMI溶液浓度,mmol/L。方程线性相关系数R2=0.9999,即准确率达到了99.99%,线性关系良好。
配置浓度为0.0715mmol/L的TBMI溶液,测其吸光度为0.253,经标准曲线计算得浓度为0.0715mmol/L,实际浓度与计算浓度相吻合,说明该检测方法灵敏可行。
实施例4
本实施例制备了1,10-双(3-甲基-1-咪唑盐基)溴代癸烷(DBMI),并绘制了相应的浓度-吸光度的标准曲线。
将0.1mol的1,10-二溴癸烷与0.21mol的N-甲基咪唑加入到盛有乙醇的圆底烧瓶中,在65℃下反应12h,反应结束冷却后有产物析出,用乙酸乙酯洗涤3次,并置于真空干燥箱中80℃烘干,即得固体产品1,10-双(3-甲基-1-咪唑盐基)溴代癸烷(DBMI),产率为86.5%。
1,10-双(3-甲基-1-咪唑盐基)溴代癸烷(DBMI):
1H-NMR(400MHz,D2O):δ8.85(s,2H),7.57(s,2H),7.51(s,2H),4.24(t,4H),3.94(s,6H),1.88(m,4H),1.29(m,12H);Elemental analysis,cal.(%):C,46.55;H,6.90;N,12.07,found(%):C,45.49;H,6.83;N,11.86。
配制浓度为0.0124mmol/L、0.0246mmol/L、0.0369mmol/L、0.0492mmol/L、0.0615mmol/L、0.0738mmol/L、0.0984mmol/L、0.123mmol/L、0.197mmol/L的9个DBMI标准溶液,用紫外-可见分光光度计在224nm处测其吸光度,以吸光度为横坐标,浓度为纵坐标,绘制标准曲线。拟合曲线,所得的标准曲线如图5所示,得DBMI标准曲线方程:y=3.25394x+0.00975,y为DBMI溶液所测得的吸光度,x为DBMI溶液浓度,mmol/L。方程线性相关系数R2=0.9999,即准确率达到了99.99%,线性关系良好。
配置浓度为0.0821mmol/L的TBMI溶液,测其吸光度为0.277,经标准曲线计算得浓度为0.0821mmol/L,实际浓度与计算浓度相吻合,说明该检测方法灵敏可行。
本发明采用一步法制备了系列短链双咪唑季铵盐,并对含有相应短链双咪唑季铵盐的溶液中的短链双咪唑季铵盐浓度进行了检测。该制备方法原料便宜易得,反应操作简单,反应时间较短、产物收率达80%以上。该检测方法操作简便、快捷、准确、高效。本发明的短链双咪唑季铵盐产品可广泛用做驱油剂、防膨剂、缓蚀剂、压裂液、粘土改性剂等,具有显著的经济效益和社会效益。
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
1.一种短链双咪唑季铵盐的制备方法,其特征在于,该制备方法包括以下步骤:
二卤代烷和N-甲基咪唑进行反应,反应结束冷却后产物析出,洗涤、干燥即得所述短链双咪唑季铵盐;
所述二卤代烷的结构式为:X-(CH2)n-X,其中X为卤素,n为2-12的整数。
2.根据权利要求1所述的制备方法,其特征在于,所述二卤代烷和N-甲基咪唑的摩尔比为1:(2.05-2.5)。
3.根据权利要求1所述的制备方法,其特征在于,所述反应的溶剂选自C2-C4的醇类、乙腈、丙酮、二氯甲烷、氯仿和乙酸乙酯中的一种或两种以上的组合。
4.根据权利要求1所述的制备方法,其特征在于,所述反应的溶剂为乙醇、异丙醇或二者的混合溶剂。
5.根据权利要求1所述的制备方法,其特征在于,所述洗涤的洗涤溶剂选自乙酸乙酯、C1-C4的醇类、乙醚、丙酮和乙腈中的一种或两种以上的组合。
6.根据权利要求1所述的制备方法,其特征在于,所述洗涤的洗涤溶剂为乙酸乙酯。
7.根据权利要求1所述的制备方法,其特征在于,所述反应的温度为55-65℃;所述反应的时间为6-18h。
8.根据权利要求1所述的制备方法,其特征在于,所述干燥为真空干燥,温度为60-80℃。
9.一种权利要求1-8所述制备方法得到的短链双咪唑季铵盐。
10.一种权利要求9所述短链双咪唑季铵盐的检测方法,其特征在于,该检测方法包括以下步骤:
制备不同浓度的短链双咪唑盐标准水溶液;
用紫外-可见分光光度计测得短链双咪唑盐的紫外最大吸收波长,并在紫外最大吸收波长处测所述短链双咪唑盐标准水溶液的吸光度;
绘制短链双咪唑盐的浓度-吸光度的标准曲线;
用紫外-可见分光光度计在短链双咪唑盐的紫外最大吸收波长处测得待测样的吸光度,所述待测样为含有短链双咪唑盐的溶液;通过测定的吸光度结合所述标准曲线计算得到待测样中短链双咪唑盐的浓度。
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