CN114105995A - 一种低共熔溶剂及其制备方法和应用 - Google Patents

一种低共熔溶剂及其制备方法和应用 Download PDF

Info

Publication number
CN114105995A
CN114105995A CN202111413323.XA CN202111413323A CN114105995A CN 114105995 A CN114105995 A CN 114105995A CN 202111413323 A CN202111413323 A CN 202111413323A CN 114105995 A CN114105995 A CN 114105995A
Authority
CN
China
Prior art keywords
acid
eutectic solvent
hydrogen bond
cellulose
eutectic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111413323.XA
Other languages
English (en)
Other versions
CN114105995B (zh
Inventor
王小慧
帅建波
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN202111413323.XA priority Critical patent/CN114105995B/zh
Publication of CN114105995A publication Critical patent/CN114105995A/zh
Application granted granted Critical
Publication of CN114105995B publication Critical patent/CN114105995B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C07C335/08—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C07C335/10—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/04—Phenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/06—Oxalic acid
    • C07C55/07—Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C07C59/08—Lactic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
    • 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
    • C07D207/18—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 one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—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 one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D211/74—Oxygen atoms
    • C07D211/76—Oxygen atoms attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C07D233/34—Ethylene-urea
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/36—One oxygen atom
    • C07D263/38—One oxygen atom attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/04—Oxycellulose; Hydrocellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2397/00—Characterised by the use of lignin-containing materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

本发明属于生物质溶剂技术领域，公开了一种低共熔溶剂及其制备方法和应用。首先制备一种超碱型离子液体，再将该离子液体作为氢键受体，和不同类型的氢键供体按照摩尔比为0.5:1～5:1进行混合，并在50～100℃加热至澄清透明，得到低共熔溶剂。与现有粘度大、成本高的离子液体以及生物质溶解性能差的低共熔溶剂相比，本发明低共熔溶剂体系不仅可以大幅度节省溶剂制备成本，而且可以显著降低体系粘度，有利于后续加工和应用。此外，本发明低共熔溶剂体系对纤维素、木质素、半纤维素等生物质原料具有优异的溶解能力，且溶解液可以应用于高性能再生薄膜材料的制备。

Description

一种低共熔溶剂及其制备方法和应用
技术领域
本发明公开了一种低共熔溶剂及其制备方法和在纤维素、半纤维素、木质素等生物质溶解方面的应用，属于生物质溶剂技术领域。
背景技术
纤维素等生物质资源来源广泛，大量存在于木材、棉、麻及谷草等植物中，是自然界中取之不尽，用之不竭的可再生资源，其有效利用可以减少有限的石油资源的使用，对经济发展和环境保护都发挥着重要的作用。然而，纤维素中存在丰富的分子内和分子间氢键，复杂的聚集态结构和结晶结构导致其无法熔融加工，也不溶于常见的溶剂。因此，纤维素溶剂的开发成为了纤维素资源高值化利用的核心。
离子液体是近年来发展的纤维素等生物质资源的有效溶剂之一，由于其具有不挥发、稳定好等优势，而被认为是绿色环保型溶剂。但现有的可用于纤维素溶解的离子液体制备流程复杂、成本较高，加之体系粘度大，溶解后的纤维素溶液粘度更大，使得该类溶剂体系制备的纤维素溶液后加工应用受限，不利于大规模化工生产应用。因此，单一的离子液体使用已经很难满足纤维素等生物质资源的溶解及后加工要求。亟待开发一种新型纤维素溶剂，该溶剂体系应具有合适粘度、利于后续加工，并且易于制备，成本合理。
低共熔溶剂，是近些年发展起来的一种新型溶剂，其性质和离子液体相似。一般由一定比例的氢键受体和氢键供体组成，氢键供体和氢键受体之间形成氢键，同时电荷发生离域，使得低共熔体系的熔点大幅降低，从而体系具有较低的粘度。由于其具有非挥发、低熔点、低毒性、可回收、易制备、低成本等优点，低共熔溶剂已被广泛应用于木质纤维素预处理。然而，低共熔溶剂在纤维素溶解方面的效果有限，仅有几篇文献报道低共熔溶剂可用于少量纤维素溶解，但都局限于低分子量纤维素(Journal of Molecular Liquids,2020,299:112140)，或需借助苛刻的溶解条件，如高温溶解(BioResources,2016,11(4):8457-8469)、强酸性溶剂体系溶解(Journal of Materials Chemistry A,2019,7(2):755-763)、超声处理(Green Energy&Environment,2020,5(2):232-239)，或含有高浓度的金属盐溶液(Carbohydrate Polymers,2021,272:118473)等，这些操作条件下不仅易造成纤维素的降解，也不适用于大规模应用。
自“禁塑令”、“双碳”政策推行以来，利用可再生、环境友好的生物质材料替代部分石油基塑料，尤其是一次性塑料制品成为广泛共识。目前，受制于绿色、低成本溶剂体系的缺失，纤维素等生物质基制品的种类和规模都非常有限。市场迫切需要针对纤维素等生物质原料开发同时具有优异溶解能力、较低粘度和低成本的新型绿色溶剂体系，推动生物质基材料产业的发展。
发明内容
本发明针对当前生物质原料，尤其是大分子量纤维素原料，溶剂体系存在的粘度高、溶解能力有限、价格昂贵、溶解条件苛刻等问题。首次提出开发一种兼具离子液体和低共熔溶剂特点的新型溶剂体系。该体系以超碱类离子液体作为氢键受体，加入氢键供体后组成低共熔溶剂，该体系的形成不仅制备简单，氢键供体来源广泛、成本低廉，而且相对传统离子液体体系的粘度显著降低，易于后处理加工，可同时实现对纤维素、半纤维素、木质素等生物质资源的高效溶解，且便于再生加工为全生物质基膜材料。
为了实现上述目的，本发明的技术方案如下：
一种低共熔溶剂，由氢键受体和氢键供体按照摩尔比为0.5:1～5:1进行混合，并在50～100℃加热至澄清透明，得到低共熔溶剂；所述氢键受体(超碱型离子液体)选自以下结构通式中的一种：
Figure BDA0003374351020000031
所述X-选自氯离子(Cl-)，溴离子(Br-),醋酸根离子(Ac-)中的一种；所述R基团选自带有不饱和键的短链烷烃。
优选地，所述R基团为烯丙基(-CH2CH＝CH2)、2-甲基烯丙基(-CH2CH3C＝CH2)或丙炔基(-CH2 C≡CH)。
优选地，所述氢键供体选自有机酸类、有机醇类、内酰胺类、酚类、脲类、氮杂环类结构中的一种或两种以上。
优选地，所述的有机酸类选自甲酸、乙酸、丙酸、正丁酸、丙烯酸、L-乳酸、D-乳酸、乙酰丙酸、甲氧基乙酸、乙氧基乙酸、α-甲基丙烯酸、D-苹果酸、L-苹果酸、D-天冬氨酸、L-天冬氨酸、D-谷氨酸、L-谷氨酸、顺丁烯二酸，反丁烯二酸、草酸、丙二酸、丁二酸、戊二酸、己二酸中的一种，其结构式如下：
Figure BDA0003374351020000041
优选地，所述的有机醇类选自乙二醇、丙三醇中的一种；其结构式如下：
Figure BDA0003374351020000042
优选地，所述的酚类选自苯酚、愈创木酚中的一种；其结构式如下：
Figure BDA0003374351020000043
所述的内酰胺类选自2-吡咯烷酮、2-噁唑烷酮、2-哌啶酮、2-咪唑烷酮、己内酰胺、丁二酰亚胺、N-羟基丁二酰亚胺中的一种，其结构式如下：
Figure BDA0003374351020000044
优选地，所述的脲类选自尿素、硫脲、甲基脲、N-甲基硫脲、乙烯硫脲、二甲基脲、二甲基硫脲、二乙基硫脲中的一种；其结构式如下：
Figure BDA0003374351020000051
优选地，所述的氮杂环类选自吗啉、咪唑、吡唑、1,2,4-三氮唑中的一种，其结构式如下：
Figure BDA0003374351020000052
优选地，所述加热温度为70～90℃。
更进一步地，本发明还提供了该低共熔溶剂在生物质溶解中的应用。
优选地，所述的生物质包括纤维素、木质素、半纤维素中的一种或两种以上。
最后，本发明还提供了该低共熔溶剂在制备再生薄膜材料中的应用。
与现有技术相比，本发明具有如下有益效果：
1.本发明通过超碱型离子液体加氢键供体形成低共熔溶剂可以大幅度节省溶剂成本，溶剂体系制备方法简单，氢键供体原料廉价易得，组分比例可调控性大，有利于推广应用。
2.本发明制备的低共熔溶剂流动性好，室温呈液体，体系粘度明显优于单一的离子液体，对不同的纤维素原料具有优异的溶解性能，溶解液粘度低，有利于后续加工和应用。
3.本发明低共熔溶剂体系不仅能有效地溶解纤维素原料，其对木质素、半纤维素等生物质原料亦具有优异的溶解能力，在生物质溶解及生物质基材料制备等方面具有潜在的应用价值。
附图说明
图1为本发明部分氢键受体核磁氢谱图，其中(a)[DBUA]Cl，(b)[DBNA]Cl。
图2为本发明制得的部分氢键受体和低共熔溶剂图片，其中(a)氢键受体[DBUA]Cl及氢键供体OxO的照片，(b)低共熔溶剂体系[DBUA]Cl/OxO的照片，(c)低共熔溶剂体系[DBUA]Cl/OxO的氢谱图。
图3(a)(b)分别为本发明低共熔溶剂[DBNA]Cl/CpL-1/1溶解微晶纤维素前、后的显微镜图片。
图4为本发明部分低共熔溶剂中制备的再生纤维素膜，其中(a)、(b)分别为低共熔溶剂[DBNA]Cl/OxO-1/1溶解木浆纤维素前、后的显微镜图片，(c)溶解纤维素后所得再生纤维素膜的XRD图谱，(d)[DBNA]Cl/OxO-1/1体系中制备得再生纤维素膜的照片。
具体实施方式
下面结合具体实施例以及附图对本发明做进一步说明。需要说明的是，以下描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域其他技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当在本申请权利要求所要求的保护范围之内。
实施例1：氢键受体[DBUA]Cl的制备，
Figure BDA0003374351020000061
在500mL二口圆底烧瓶中，加入超碱原料1,8-二氮杂二环[5.4.0]十一碳-7-烯91.2g(0.6mol,1.0eq.)和80mL丙酮，0℃低温浴下不断搅拌。往上述溶液中滴加50.5g(0.66mol,1.1eq.)烯丙基氯，滴加完毕后，于55℃条件下搅拌6h。反应结束后，冷却至室温，减压蒸除溶剂，得浅黄色粉末状固体134.7g，产率98.5％。产物的结构由核磁氢谱确定，其谱图如附图1(a)所示。1H NMR(600MHz,DMSO-d6)δ5.92–5.85(m,1H),5.30–5.21(m,2H),4.26(dt,J＝4.5,1.6Hz,2H),3.73–3.68(m,2H),3.56(t,J＝5.9Hz,2H),3.47–3.43(m,2H),2.87–2.82(m,2H),2.03–1.98(m,2H),1.72–1.60(m,6H).
实施例2：氢键受体[DBNA]Cl的制备，
Figure BDA0003374351020000071
在500mL二口圆底烧瓶中，加入超碱原料1,5-二氮杂双环[4,3,0]壬-5-烯62.1g(0.5mol,1.0eq.)和70mL丙酮，0℃低温浴下不断搅拌。往上述溶液中滴加42.1g(0.55mol,1.1eq.)烯丙基氯，滴加完毕后，于55℃条件下搅拌6h。反应结束后，冷却至室温，减压蒸除溶剂，得浅黄色固体98.4g，产率98.2％。产物的结构由核磁氢谱确定，其谱图如附图1(b)所示。1H NMR(600MHz,DMSO-d6))δ5.92(ddt,J＝17.1,10.4,5.6Hz,1H),5.36(dq,J＝17.2,1.5Hz,1H),5.27(dd,J＝10.3,1.4Hz,1H),4.15(d,J＝5.6Hz,2H),3.77–3.68(m,2H),3.42(dt,J＝17.6,5.8Hz,4H),3.10(t,J＝8.0Hz,2H),2.08–1.98(m,4H).
实施例3：本发明部分低共熔溶剂体系的制备，
取实施例1中制备的氢键受体[DBUA]Cl(2.28g,1.00mmol)于30mL香精瓶中，加入2-噁唑烷酮OxO(0.87g,1.00mmol)，加热至90℃，并不断搅拌。加热2h后，固体状态的[DBUA]Cl和OxO可转化成澄清透明的低共熔溶剂，记为[DBUA]Cl/OxO-1/1。改变[DBUA]Cl：OxO的比例为2：1，3：1，4：1，可以得到不同配比的低共熔溶剂体系，分别记为[DBUA]Cl/OxO-2/1，[DBUA]Cl/OxO-3/1，[DBUA]Cl/OxO-4/1。
如图2所示，氢键受体[DBUA]Cl及氢键供体OxO分别为浅黄色粉末状固体和白色粉末状固体(a)，不同比例的[DBUA]Cl与OxO混合加热后可得到澄清透亮的低共熔溶剂(b)，且供体OxO比例越大时，低共熔体系的流动性越好，粘度越低。由图2(c)各物质的氢谱数据可知，所得低共熔体系[DBUA]Cl/OxO-1/1，[DBUA]Cl/OxO-4/1的氢谱只是受体[DBUA]Cl和供体OxO谱图的叠加，并无新物质峰的形成，且OxO谱图中的N-H峰(化学位移7.6ppm附近)发生了偏移，且受体[DBUA]Cl量越多偏移越明显，说明供体OxO与受体[DBUA]Cl形成了强氢键作用，使得体系粘度降低。由此可以证明，本发明将离子液体作为氢键受体，加入氢键供体后形成低共熔溶剂体系的可行性。
其它低共熔溶剂体系亦可用上述方法制得，表1中列举了本发明其它部分低共熔溶剂的所用到的氢键供体，氢键受体以及它们的配比及编号。
表1本发明部分低共熔溶剂体系
Figure BDA0003374351020000081
Figure BDA0003374351020000091
Figure BDA0003374351020000101
实施例4：本发明所得低共熔溶剂的粘度值测量，
取实施例3中制备的部分低共熔溶剂体系100g，通过油浴加热控制溶剂体系的温度，采用旋转粘度计(上海力辰)测量溶剂体系在不同温度值的粘度值，控制粘度计的升降开关将转子浸入溶剂体系中至转子杆上的凹槽刻痕处，选择合适的转子和转速，使扭矩百分读数在10～90％之间，每个温度值下的粘度值测量三次并取平均值，测试结果如表2所示。
表2本发明部分低共熔溶剂体系的粘度值
Figure BDA0003374351020000102
Figure BDA0003374351020000111
注：s表明该温度下为固体
由表2可知，氢键受体[DBUA]Cl在测量温度范围内均为固体状态，故无粘度值。通过加入氢键供体后，所得体系在室温下呈液体状态，且粘度值随着温度的升高而逐渐下降。氢键受体[DBNA]Cl在70℃以上为液体，但是其粘度值较大，溶解纤维素等生物质原料后的流动性不好，不利于溶解液的后续加工。通过在[DBNA]Cl加入不同氢键供体后可明显降低共熔体系的粘度值，如低共熔体系[DBNA]Cl/MeA-2/1、[DBNA]Cl/OxO-1/1、[DBNA]Cl/PyO-1/1、[DBNA]Cl/HeO-1/1在60℃以上的粘度值均低于100mPa·s，对于生物质原料的溶解及后加工都具有非常大的优势。
实施例5：本发明所得低共熔溶剂对生物质原料的溶解，
本测试例采用微晶纤维素(国药)、磨木木质素、半纤维素(源叶生物)测定本发明低共熔溶剂体系对纤维素、木质素、半纤维素的溶解性能。具体测试方法为：取实施例3中制备的部分低共熔溶剂各3g，加入60mg微晶纤维素样品，加热至90℃搅拌溶解，1h后用玻璃棒蘸取少量溶解液于载玻片上，置于光学显微镜下观察溶解情况。判断溶解后，继续加入微晶纤维素并重复上述显微镜观察步骤。直至溶解液变粘稠时(搅拌子速度变慢)，减少纤维素加入量至每次10mg，重复镜检观察溶解情况，直至显微镜图像中有不溶解的纤维素原料时停止加入纤维素，并累计纤维素加入量，除以低共熔溶剂量(3g)即得该低共熔溶剂体系对纤维素的质量百分溶解度。同理，木质素、半纤维素的溶解度测试方法也可按照上述测试纤维素溶解度的方法进行测定，测试结果如表3所示。
表3本发明部分低共熔溶剂对生物质原料的溶解性能
Figure BDA0003374351020000121
Figure BDA0003374351020000131
注：s表明该测试温度下溶剂为固体
如图3所示，本发明低共熔溶剂[DBNA]Cl/CpL-1/1溶解微晶纤维素(8wt％)后的显微镜照片中已无纤维素存在，说明该溶剂体系对纤维素的有效溶解。由表3可知，本发明部分低共熔溶剂体系对纤维素具有优异的溶解性能。如溶剂[DBNA]Cl/PyO-1/1、[DBNA]Cl/HeO-1/1、[DBNA]Cl/MoL-1/1、[DBNA]Cl/DmU-2/1等溶剂对纤维素的溶解度达15wt％以上，虽然溶解度不及受体[DBNA]Cl(溶解度：17.1wt％)，但含氢键供体的低共熔体系溶解纤维素之后的溶解液粘度要远低于受体[DBNA]Cl，对于溶解液的后处理加工及材料制备等更具优势。而且，氢键供体的引入可以大幅度节省溶剂成本。
除了纤维素，本发明低共熔溶剂体系对木质素、半纤维素等生物质原料也具有优异的溶解性能，如[DBNA]Cl/CpL-1/1、[DBNA]Cl/OxO-1/1、[DBNA]Cl/ImO-2/1、[DBNA]Cl/PyO-1/1等低共熔溶剂体系对木素的溶解度达80wt％以上，高于受体[DBNA]Cl对木素的溶解度(48.3wt％)。[DBNA]Cl/PeO-2/1、[DBNA]Cl/CpL-1/1、[DBNA]Cl/PyO-1/1、[DBNA]Cl/MeU-2/1、[DBNA]Cl/MeT-2/1等低共熔溶剂体系对半纤维素的溶解度高于20wt％，高于纯受体[DBNA]Cl对半纤维素的溶解度(6.2wt％)。上述测试结果表明本发明低共熔溶剂体系对纤维素、木质素、半纤维素等生物质原料具有显著的溶解性能，溶解度接近或高于只含受体的溶剂体系。与现有离子液体溶剂相比，氢键供体的引入不仅降低了溶剂成本，还降低了体系粘度，有利于溶解液的后续加工。
实施例6：本发明所得低共熔溶剂体系中再生纤维素膜的制备，
本测试例采用实施例3中部分低共熔溶剂及针叶木溶解浆制备再生纤维素膜材料。具体做法为：取低共熔溶剂体系14g，加热至90℃搅拌均匀后加入0.28g针叶木溶解木浆，搅拌溶解2h。待其溶解后，静置脱泡30min，随后将溶解液倒入玻璃皿中延流成膜。室温静置6h后将膜置于去离子水中凝固，并用去离子水洗涤除去溶剂，经平板干燥器干燥后即可得再生纤维素膜。
如图4(a)、(b)所示，将原料木浆经低共熔溶剂[DBNA]Cl/OxO-1/1溶解后，溶解液的显微镜照片中已无木浆纤维素存在，说明本发明低共熔溶剂[DBNA]Cl/OxO-1/1不仅能有效溶解微晶纤维素，亦能溶解高分子量的木浆纤维素。图4(c)展示了本发明低共熔溶剂[DBNA]Cl/OxO-1/1、[DBNA]Cl/CpL-1/1、[DBNA]Cl/PyO-1/1、[DBNA]Cl/HeO-1/1体系中制备得到的再生纤维素膜的XRD图谱，由图可知经以上溶剂溶解再生后，木浆纤维素的晶型由纤维素Ⅰ转变为纤维素Ⅱ。图4(d)显示了本发明低共熔溶剂[DBNA]Cl/OxO-1/1体系中制备的再生纤维素膜的照片，该膜具有优异的机械强度(拉伸应力118.3MPa，断裂伸长率14.2％)以及透光率(可见光区大于90％)，有望应用于食品、日化品等包装领域。

Claims (10)

1.一种低共熔溶剂，其特征在于，由氢键受体和氢键供体按照摩尔比为0.5:1～5:1进行混合，并在50～100℃加热至澄清透明，得到低共熔溶剂；所述氢键受体选自以下结构通式中的一种：
Figure FDA0003374351010000011
所述X-选自氯离子(Cl-)，溴离子(Br-),醋酸根离子(Ac-)中的一种；所述R基团选自带有不饱和键的短链烷烃。
2.根据权利要求1所述的低共熔溶剂，其特征在于，所述R基团为烯丙基(-CH2CH＝CH2)、2-甲基烯丙基(-CH2CH3C＝CH2)或丙炔基(-CH2C≡CH)。
3.根据权利要求1或2所述的低共熔溶剂，其特征在于，所述氢键供体选自有机酸类、有机醇类、内酰胺类、酚类、脲类、氮杂环类结构中的一种或两种以上。
4.根据权利要求3所述的低共熔溶剂，其特征在于，所述的有机酸类选自甲酸、乙酸、丙酸、正丁酸、丙烯酸、L-乳酸、D-乳酸、乙酰丙酸、甲氧基乙酸、乙氧基乙酸、α-甲基丙烯酸、D-苹果酸、L-苹果酸、D-天冬氨酸、L-天冬氨酸、D-谷氨酸、L-谷氨酸、顺丁烯二酸，反丁烯二酸、草酸、丙二酸、丁二酸、戊二酸、己二酸中的一种。
5.根据权利要求4所述的低共熔溶剂，其特征在于，所述的有机醇类选自乙二醇、丙三醇中的一种；所述的酚类选自苯酚、愈创木酚中的一种；所述的内酰胺类选自2-吡咯烷酮、2-噁唑烷酮、2-哌啶酮、2-咪唑烷酮、己内酰胺、丁二酰亚胺、N-羟基丁二酰亚胺中的一种。
6.根据权利要求5所述的低共熔溶剂，其特征在于，所述的脲类选自尿素、硫脲、甲基脲、N-甲基硫脲、乙烯硫脲、二甲基脲、二甲基硫脲、二乙基硫脲中的一种；所述的氮杂环类选自吗啉、咪唑、吡唑、1,2,4-三氮唑中的一种。
7.根据权利要求6所述的低共熔溶剂，其特征在于，所述加热温度为70～90℃。
8.权利要求1～7任意一项所述的低共熔溶剂在生物质溶解中的应用。
9.根据权利要求8所述的应用，其特征在于，所述的生物质包括纤维素、木质素、半纤维素中的一种或两种以上。
10.根据权利要求1～7任意一项所述的低共熔溶剂在制备再生薄膜材料中的应用。
CN202111413323.XA 2021-11-25 2021-11-25 一种低共熔溶剂及其制备方法和应用 Active CN114105995B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111413323.XA CN114105995B (zh) 2021-11-25 2021-11-25 一种低共熔溶剂及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111413323.XA CN114105995B (zh) 2021-11-25 2021-11-25 一种低共熔溶剂及其制备方法和应用

Publications (2)

Publication Number Publication Date
CN114105995A true CN114105995A (zh) 2022-03-01
CN114105995B CN114105995B (zh) 2022-12-16

Family

ID=80372946

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111413323.XA Active CN114105995B (zh) 2021-11-25 2021-11-25 一种低共熔溶剂及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN114105995B (zh)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702697A (zh) * 2022-04-26 2022-07-05 中国林业科学研究院林产化学工业研究所 基于低共熔溶剂的半纤维素基水凝胶及其制备方法和应用
CN114835921A (zh) * 2022-05-23 2022-08-02 华南理工大学 一种低共熔溶剂及其制备方法与应用
CN114950485A (zh) * 2022-04-11 2022-08-30 齐鲁理工学院 一种低共熔溶剂辅助合成的NiS/VS2复合材料及其应用
CN115449136A (zh) * 2022-09-29 2022-12-09 浙江大学 一种橡胶纳米复合材料的促进剂组合物及其制备方法和应用
CN116230104A (zh) * 2023-05-09 2023-06-06 青岛科技大学 基于分子动力学和多变量分析的低共熔溶剂筛选方法
CN116283516A (zh) * 2023-03-27 2023-06-23 宁夏中星显示材料有限公司 一种低共熔溶剂及其制备方法和应用
WO2023208257A1 (zh) * 2022-04-29 2023-11-02 齐鲁工业大学(山东省科学院) 一种改善再生纤维素纤维表面结构的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105970346A (zh) * 2016-05-26 2016-09-28 中国科学院过程工程研究所 杂双环离子液体同时溶解动物毛和高分子助剂制备纺丝液的方法
CN107899371A (zh) * 2017-12-27 2018-04-13 中国科学院过程工程研究所 一种新型高效可逆吸收氨气的离子型低共熔溶剂
CN110540508A (zh) * 2019-08-30 2019-12-06 齐鲁工业大学 一种低共熔溶剂及其在提取木质素中的应用
CN112979936A (zh) * 2021-02-08 2021-06-18 中国科学院过程工程研究所 一种低共熔溶剂作为催化剂制备聚碳酸酯的方法
CN113265072A (zh) * 2021-05-19 2021-08-17 华南理工大学 一种溶解纤维素的低共熔溶剂及其溶解纤维素的方法
CN113461975A (zh) * 2021-06-29 2021-10-01 江苏大学 一种氯化胆碱低共熔溶剂及其制备方法和应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105970346A (zh) * 2016-05-26 2016-09-28 中国科学院过程工程研究所 杂双环离子液体同时溶解动物毛和高分子助剂制备纺丝液的方法
CN107899371A (zh) * 2017-12-27 2018-04-13 中国科学院过程工程研究所 一种新型高效可逆吸收氨气的离子型低共熔溶剂
CN110540508A (zh) * 2019-08-30 2019-12-06 齐鲁工业大学 一种低共熔溶剂及其在提取木质素中的应用
CN112979936A (zh) * 2021-02-08 2021-06-18 中国科学院过程工程研究所 一种低共熔溶剂作为催化剂制备聚碳酸酯的方法
CN113265072A (zh) * 2021-05-19 2021-08-17 华南理工大学 一种溶解纤维素的低共熔溶剂及其溶解纤维素的方法
CN113461975A (zh) * 2021-06-29 2021-10-01 江苏大学 一种氯化胆碱低共熔溶剂及其制备方法和应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
WEI HUI等: "Protic ionic liquids tailored by different cationic structures for efficient chemical fixation of diluted and waste CO2 into cyclic carbonates", 《NEW JOURNAL OF CHEMISTRY》 *
WENQUAN ZHANG等: "Super-base-derived hypergolic ionic fuels with remarkably improved thermal stability", 《JOURNAL OF MATERIALS CHEMISTRY A: MATERIALS FOR ENERGY》 *
WU, LINGQIAO等: "Very efficient conversion of glucose to 5-hydroxymethylfurfural in DBU-based ionic liquids with benzenesulfonate anion", 《GREEN CHEMISTRY》 *
YUNHEJIN等: "Cationic effect on properties related to thermal stability and ignition delay for hypergolic ionic liquids", 《JOURNAL OF MOLECULAR LIQUIDS》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114950485A (zh) * 2022-04-11 2022-08-30 齐鲁理工学院 一种低共熔溶剂辅助合成的NiS/VS2复合材料及其应用
CN114950485B (zh) * 2022-04-11 2023-05-09 齐鲁理工学院 一种低共熔溶剂辅助合成的NiS/VS2复合材料及其应用
CN114702697A (zh) * 2022-04-26 2022-07-05 中国林业科学研究院林产化学工业研究所 基于低共熔溶剂的半纤维素基水凝胶及其制备方法和应用
WO2023208257A1 (zh) * 2022-04-29 2023-11-02 齐鲁工业大学(山东省科学院) 一种改善再生纤维素纤维表面结构的方法
CN114835921A (zh) * 2022-05-23 2022-08-02 华南理工大学 一种低共熔溶剂及其制备方法与应用
CN114835921B (zh) * 2022-05-23 2024-04-30 华南理工大学 一种低共熔溶剂及其制备方法与应用
CN115449136A (zh) * 2022-09-29 2022-12-09 浙江大学 一种橡胶纳米复合材料的促进剂组合物及其制备方法和应用
CN115449136B (zh) * 2022-09-29 2024-02-27 浙江大学 一种橡胶纳米复合材料的促进剂组合物及其制备方法和应用
CN116283516A (zh) * 2023-03-27 2023-06-23 宁夏中星显示材料有限公司 一种低共熔溶剂及其制备方法和应用
CN116283516B (zh) * 2023-03-27 2023-11-14 宁夏中星显示材料有限公司 一种低共熔溶剂及其制备方法和应用
CN116230104A (zh) * 2023-05-09 2023-06-06 青岛科技大学 基于分子动力学和多变量分析的低共熔溶剂筛选方法
CN116230104B (zh) * 2023-05-09 2023-08-22 青岛科技大学 基于分子动力学和多变量分析的低共熔溶剂筛选方法

Also Published As

Publication number Publication date
CN114105995B (zh) 2022-12-16

Similar Documents

Publication Publication Date Title
CN114105995B (zh) 一种低共熔溶剂及其制备方法和应用
CN102924698B (zh) 用于聚对苯二甲酸丁二醇酯合成的钛系催化剂制备方法及应用
CA2953273A1 (en) Alkaline laundry liquid composition comprising polyesters
EP3720838A1 (en) Organic sulfonic acid salts of amino acid esters and process for their preparation
CN108003332B (zh) 一种易水解聚酯及其合成方法
CN101665515B (zh) P-n协同型阻燃化合物及其制备方法
CN114835921B (zh) 一种低共熔溶剂及其制备方法与应用
CN104059215A (zh) 一种tdi异氰脲酸酯的制备方法
CN103709679B (zh) 一种改性脂肪族-芳香族共聚酯及其制备方法和应用
CN103044237A (zh) 一种高效转化纤维素制备乙酰丙酸的方法
CN109851821B (zh) 一种能够有效溶解超支化聚酯的低共熔溶剂及其溶解方法
CN111718425B (zh) 一种可熔融加工的纤维素酯及其制备方法与应用
CN103665788B (zh) 一种改性pet共聚酯及其制备方法和应用
US4647680A (en) Water-soluble titanium acetylacetonates
CN102584883A (zh) 含多硅的甲基丙烯酸酯和丙烯酸酯类单体及合成方法
CN101125819A (zh) 十八伯胺聚氧乙烯醚的合成方法
CN102432861A (zh) 一种支化聚醚大单体及其制备方法
CN114016297A (zh) 一种低黄变亲水硅油乳液及其制备方法
CN107840942B (zh) 含三嗪三酮环结构的咪唑类潜伏性固化剂及其制备方法
CN114195791A (zh) 一种多元离子液体及其制备方法和应用
CN115612032A (zh) 一种丙烯酸类增稠剂的合成方法
CN113501962A (zh) 一种低黄变亲水嵌段聚醚氨基硅油及其制备方法
CN108424534B (zh) 一种能够溶解聚乙二醇的低共熔溶剂及其溶解方法
CN103073919A (zh) 一种溶剂黄33
KR100889373B1 (ko) 이온성 액체에 용해된 셀룰로오즈 용액

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant