CN114436968A - Ionic liquid plasticizer, and preparation method and application thereof - Google Patents
Ionic liquid plasticizer, and preparation method and application thereof Download PDFInfo
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- CN114436968A CN114436968A CN202111600390.2A CN202111600390A CN114436968A CN 114436968 A CN114436968 A CN 114436968A CN 202111600390 A CN202111600390 A CN 202111600390A CN 114436968 A CN114436968 A CN 114436968A
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 67
- 239000004014 plasticizer Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 26
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 150000003852 triazoles Chemical class 0.000 claims abstract description 15
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- 239000012074 organic phase Substances 0.000 claims abstract description 5
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 15
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- 239000001257 hydrogen Substances 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 229910052799 carbon Inorganic materials 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- -1 trifluoromethanesulfonimide anion Chemical class 0.000 description 17
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 230000003993 interaction Effects 0.000 description 9
- 229920002635 polyurethane Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PRSVVQUTQFCLLA-UHFFFAOYSA-N 1-(2-methoxyethyl)-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].COCC[NH+]1CN(C)C=C1 PRSVVQUTQFCLLA-UHFFFAOYSA-N 0.000 description 2
- XTIGGAHUZJWQMD-UHFFFAOYSA-N 1-chloro-2-methoxyethane Chemical compound COCCCl XTIGGAHUZJWQMD-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- OIYZZWJVQSTXHW-UHFFFAOYSA-N COCCN(C1)C=CN1C=C.Br Chemical compound COCCN(C1)C=CN1C=C.Br OIYZZWJVQSTXHW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 1
- YVXWWIPQSJWDAL-UHFFFAOYSA-N 1-(2-methoxyethyl)-3-methyl-2h-imidazole Chemical compound COCCN1CN(C)C=C1 YVXWWIPQSJWDAL-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- GPTVQTPMFOLLOA-UHFFFAOYSA-N 1-chloro-2-ethoxyethane Chemical compound CCOCCCl GPTVQTPMFOLLOA-UHFFFAOYSA-N 0.000 description 1
- MWZDIEIXRBWPLG-UHFFFAOYSA-N 1-methyl-1,2,4-triazole Chemical compound CN1C=NC=N1 MWZDIEIXRBWPLG-UHFFFAOYSA-N 0.000 description 1
- CIDRJNRCHQJEPC-UHFFFAOYSA-N C(C)(=O)O[N+]1=CN(C=C1)C Chemical compound C(C)(=O)O[N+]1=CN(C=C1)C CIDRJNRCHQJEPC-UHFFFAOYSA-N 0.000 description 1
- UXMOSEAGPUYKDL-UHFFFAOYSA-M CC(ON1C=[N+](C=C)C=C1)=O.[Cl-] Chemical compound CC(ON1C=[N+](C=C)C=C1)=O.[Cl-] UXMOSEAGPUYKDL-UHFFFAOYSA-M 0.000 description 1
- 125000002038 D-arginyl group Chemical group N[C@@H](C(=O)*)CCCNC(=N)N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OXUYYRIDSBUUJQ-UHFFFAOYSA-N ethyl 1H-imidazole-2-carboxylate hydrochloride Chemical compound CCOC(=O)C1=NC=CN1.Cl OXUYYRIDSBUUJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001617 migratory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
- C07D233/60—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 hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/05—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing at least three cyano groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
-
- 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
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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Abstract
The invention provides an ionic liquid plasticizer, a preparation method and application thereof, which are used for solving the technical problem that the plasticizer is easy to migrate from a product, wherein the ionic liquid consists of anions and cations, and the preparation method of the ionic liquid plasticizer comprises the following steps: adding an imidazole or triazole precursor, a halide RX and a solvent A into a reaction vessel, stirring for reaction, separating liquid after the reaction is finished, washing and extracting to obtain an organic phase, and removing the solvent to obtain an ionic liquid I; adding the ionic liquid I obtained in the step (1), inorganic salt and a solvent B into a reaction container for reaction, obtaining a precipitate after the reaction, washing, removing the solvent, and drying to obtain an ionic liquid plasticizer; the ionic liquid obtained by the invention is used as a plasticizer of polyurethane and epoxy resin, and the cured product has better heat resistance and migration resistance, and can obviously increase the elongation at break of the product, increase the toughness of the product and reduce the brittleness on the premise of keeping the tensile strength to be increased in a small range.
Description
Technical Field
The invention relates to an ionic liquid plasticizer, and particularly relates to an ionic liquid plasticizer, a preparation method and application thereof.
Background
The plasticizer plays a vital role in plastic products in the plastic processing industry, is used as a high-molecular auxiliary material additive, and is applied to various fields of national economy, such as rubber, plastics, cellulose, resin, medical equipment, cables and other products. The plasticizer is added into the plastic processing, so that the plastic processing is more flexible and easy to process, and can greatly meet the requirements of people.
The plasticizers used in the current polymers are mainly phthalate esters and other esters, diethyl phthalate (DOP) and di (2-ethylhexyl) adipate (DOA) are common plasticizer types, but DOP has high toxicity and is a carcinogen, the long-term contact of certain phthalate esters can inhibit and paralyze the central nervous system of human, even can damage organs such as reproduction, liver, kidney and the like, and the DOA is easy to migrate from the product, and the DOA is more migratory than the DOP. When the plasticizer and the polymer are not completely mixed, a large gap is formed between the plasticizer and the polymer in a shear rate area, plasticizer molecules migrate to a high shear rate area and form an obvious slip layer, and the viscoplastic flow behavior generated by the migration is influenced by the interaction of the polymer and the plasticizer, so that the processing performance and the plasticity of the polyurethane system are greatly influenced.
The ionic liquid consists of anions and cations, is a liquid low-melting-point molten salt at room temperature, has extremely low vapor pressure, is stable to water and air, and can be used as a green solvent and adjusted according to specific structures and chemical properties; and the ionic liquid as a polar solvent can be well compatible with a polymer system, and the ionic liquid plasticizer is a new direction for the research in the field of plasticizers. However, the application of the ionic liquid as the plasticizer is very small at present, so that the ionic liquid used as the plasticizer of the epoxy resin has a great application prospect.
Disclosure of Invention
Aiming at the technical problems that diethyl phthalate (DOP) and di (2-ethylhexyl) adipate (DOA) plasticizers can cause harm to human bodies and easily migrate from products, the invention provides a novel ionic liquid plasticizer, the ionic liquid is used as a plasticizer for polyurethane and epoxy resin, and the cured products have good heat resistance and migration resistance, so that the aim of enhancing the strength of the materials is fulfilled.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
an ionic liquid plasticizer, wherein the ionic liquid is composed of anions and cations, and the cations of the ionic liquid are any one of the following structures:
the ionic liquid anion is any one of the following structures:
the density of the ionic liquid is more than or equal to 1.00g cm < -1 >, and the melting point is lower than-50 ℃.
The preparation method of the ionic liquid plasticizer comprises the following steps:
(1) adding an imidazole or triazole precursor, a halide RX and a solvent A into a reaction vessel, stirring for reaction, separating liquid after the reaction is finished, washing and extracting to obtain an organic phase, and removing the solvent to obtain an ionic liquid I;
r is
X is a halogen atom;
(2) adding the ionic liquid I obtained in the step (1), inorganic salt and a solvent B into a reaction container for reaction, obtaining a precipitate after the reaction, washing, removing the solvent, and drying to obtain an ionic liquid plasticizer; the anion of the inorganic salt is any one of the following structures, the cation is Li + or Ag +,
the molar ratio of the imidazole or triazole to the halide R1 in the step (1) is 1: (1-2).
The reaction temperature in the step (1) is 25-30 ℃, and the reaction time is 12-24 h.
In the step (1), X is Br or Cl.
The molar ratio of the ionic liquid to the inorganic salt in the step (2) is 1 (1-1.4).
The reaction temperature in the step (2) is 25-110 ℃, and the reaction time is 12-48 h.
The solvent A is any one of ethyl acetate, acetonitrile or tetrahydrofuran, and the solvent B is deionized water or methanol.
The novel ionic liquid plasticizer is applied to the field of polyurethane or epoxy resin, and the addition amount of the ionic liquid plasticizer is 3-8% of the formula mass.
The invention has the beneficial effects that: the ionic liquid structure takes an imidazole and triazole structure as a cation matrix, optimizes the structure by using a straight-chain ether group or an ester group, and then matches the structure with different anions to finally obtain an ionic liquid plasticizer; the prepared ionic liquid plasticizer contains polar groups and nonpolar groups, and the matrix contains ether groups or ester groups, so that the compatibility and the processing performance of the ionic liquid plasticizer with polyurethane and epoxy resin systems are improved as the plasticizer; in addition, the ionic liquid plasticizer strengthens the linkage with polyurethane molecules through the action of hydrogen bonds, improves the toughness and reduces the mobility of plasticizer molecules; in addition, the trifluoromethanesulfonimide anion contains a C-F bond and a sulfur-oxygen bond, and the tetrafluoroborate radical contains a B-F bond, so that hydrogen bonds or electrostatic interaction can be generated with an epoxy resin system interface, the adhesion is increased, and the migration effect is reduced; due to the asymmetry of the anion and cation structures, the prepared ionic liquid is liquid at room temperature, and the high-temperature stability of an epoxy resin system can be improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the effect of curing HTPB and TDI, ionic liquid systems;
FIG. 2 is an Independent Gradient Model (IGM) scattergram;
FIG. 3 is a three-dimensional graph of the interaction of polyurethane and ionic liquid with IGM.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
An ionic liquid plasticizer containing imidazole and triazole structures is prepared by the following steps:
1-methyl-3-methoxyethyl imidazole NTf2Salt:
in the first step, chloroethyl methyl ether (30mL, 0.4mol) was dissolved in ethyl acetate and the mixture was added to 1-methylimidazole (32mL, 0.4 mol). The mixture was stirred with heating at 50 ℃ for 12h and cooled to room temperature. After washing three times with 70mL ethyl acetate and removal of the solvent by rotary evaporation, the residual liquid (61.4g, 95%) solidified at room temperature to give 1-methyl-3-methoxyethylimidazole chloride salt.
In the second step, lithium bistrifluoromethanesulfonate (112.46g, 0.4mol) was weighed and dissolved in 100mL of deionized water, and 1-methyl-3-methoxyethyl imidazole chloride (54.35g, 0.3mol) was weighed and dissolved in 100mL of deionized water. The two are mixed and stirred in a flask and stirred for 24 hours at 25 ℃, and light yellow oily water-insoluble liquid is generated after the reaction. The liquid was subjected to a liquid separation operation and water in the ionic liquid was removed by rotary evaporation to give a product (113.67g, 89%).
The purity of the aqueous product was determined by hydrogen spectroscopy, which gave the following 1H NMR (600MHz, DMSO): 9.57(s,1H, CH) is the hydrogen evolution peak position on carbon at position No. 2 on the imidazole ring, 7.91(t, J ═ 1.90Hz,1H, CH) is the hydrogen evolution peak position on carbon at position No. 3 on the imidazole ring, 7.85(t, J ═ 1.90Hz,1H, CH) is the hydrogen evolution peak position on carbon at position No. 4 on the imidazole ring, 4.42(t, J ═ 5.05Hz,2H, CH2) is the hydrogen evolution peak position on carbon at position No. 6, 3.90(s,3H, CH3) is the hydrogen evolution peak position on carbon at position No. 7, 3.71(t, J ═ 5.05Hz,2H, CH2) is the hydrogen evolution peak position on carbon at position No. 5, and 3.24(s,3H, CH3) is the hydrogen evolution peak position on carbon at position No. 1. 13CNMR (151MHz, DMSO): 160.52, 154.12 is the position of the C peak on NTf2, 136.93 is the carbon at position 2, 123.33 is the carbon at position 3, 122.51 is the carbon at position 4, 69.52 is the carbon at position 6, 57.93 is the carbon at position 5, 48.36 is the carbon at position 7, 35.61 is the carbon at position 1. The infrared spectrum is IR (KBr) cm-1: 3391, 3072, 1570, 1449, 1177, 1117, 1013, 832. Elemental analysis for C7H13ClN2O (%): c47.60, H7.42, N15.86, O9.06; experimental values: the purity of C47.82, H7.35, N15.68 and O9.12 is proved to be excellent by the difference with the theoretical value.
Example 2
1-methyl-3-methoxyethyl-1, 2, 4-triazole bistrifluoromethylsulfonyl imide salt.
Firstly, weighing 1-methyl-1, 2, 4-triazole (48.468g, 0.583mol) and dissolving in 50mL ethyl acetate; chloroethyl methyl ether (68.214g, 0.722mol) was weighed out and dissolved in 50mL ethyl acetate before being added to the triazole solution. Stirring the mixed solution for 48h at 100 ℃, carrying out rotary evaporation, and removing the solvent to generate yellow liquid, namely the 1-methyl-3-methoxyethyl-1, 2, 4-triazole chloride salt.
In the second step, 1-methyl-3-methoxyethyl-1, 2, 4-triazolium chloride (70.899g, 0.399mol) was weighed out and dissolved in 80mL of deionized water. Lithium bistrifluoromethanesulfonylimide (126.134g, 0.439mol) was weighed out and dissolved in 100mL of deionized water, and then added to a 1-methyl-3-methoxyethyl-1, 2, 4-triazole chloride salt solution. Stirring the mixed solution at normal temperature for 12h to form two layers, wherein the upper layer is a deionized water phase, and the lower layer is a yellow liquid. The lower organic phase was washed with deionized water several times, an appropriate amount of anhydrous magnesium sulfate was added, and the organic phase was dissolved with methanol. Standing the solution at low temperature overnight, filtering, and rotary steaming to obtain yellow liquid, i.e. 1-methyl-3-methoxyethyl-1, 2, 4-triazole NTf2Salt (105.914g, 62.79% yield).
The hydrogen spectra were obtained experimentally by 1H NMR (600MHz, DMSO): delta 10.02(s,1H, CH) indicates the hydrogen peak at position 2 on triazole9.14(s,1H, CH) is the hydrogen peak at position 3 on triazole, 4.46-4.44 (m,2H, CH2) is the hydrogen peak at position 4, 4.08(s,3H, CH3) is the hydrogen peak at position 6, 3.72-3.70 (m,2H, CH2) is the hydrogen peak at position 5, and 3.30ppm (s,3H, CH3) is the hydrogen peak at position 1. 13C NMR (151MHz, DMSO) δ — 145.88 is carbon No. 2 on triazole, 144.13 is carbon No. 3 on triazole, 123.15, 121.02, 118.89, 116.75 is the carbon-peak position on NTf2-, 62.65 is carbon No. 5, and 48.57 is carbon No. 1, in ppm. The infrared spectrum peak position is IR (KBr): nu is 3147, 1583, 1351, 1393, 1137, 1056, 1015, 790, 740, 664, 643, 617, 571, 514cm-1. Elemental analysis for C8H12F6N4O5S2 (%): c22.75, H2.86, N13.27, S15.18; actual values: the purity of C22.91, H2.54, N13.53 and S14.96 is proved to be excellent by the difference with the theoretical value.
Example 3
1-methyl-3-methoxyethyl-1, 2, 4-triazole nitrate
The preparation of 1-methyl-3-methoxyethyl-1, 2, 4-triazolium chloride was carried out in the same manner as in example 2;
firstly, weighing (84.904g, 0.478mol) 1-methyl-3-methoxyethyl-1, 2, 4-triazole chloride salt and dissolving in 100mL deionized water; silver nitrate (81.280g, 0.478mol) was weighed out and dissolved in 100mL of deionized water. And mixing the two solutions to prepare a mixed solution, stirring the mixed solution at normal temperature for 12 hours to generate a white precipitate, filtering, performing rotary evaporation, and performing vacuum drying to obtain a crude product. Dropwise adding NaCl to remove excessive AgCl, heating to 60 ℃, adding excessive acetonitrile, refrigerating for 24h in a refrigerator, filtering, and rotary steaming. This was repeated several times to obtain the final product (73.012g, yield 74.83%).
And (3) carrying out hydrogen spectrum, carbon spectrum, infrared and element analysis tests on the result to obtain: hydrogen spectrum 1H NMR (600MHz, DMSO): delta is 10.02(s,1H, CH) and is the hydrogen peak at position 2 on triazole, 9.14(s,1H, CH) is the hydrogen peak at position 3 on triazole, 4.46-4.44 (m,2H, CH2) is the hydrogen peak at position 4, 4.08(s,3H, CH3) is the hydrogen peak at position 6, 3.72-3.70 (m,2H, CH2) is the hydrogen peak at position 5The peak is shown, 3.30ppm (s,3H, CH3) is the hydrogen peak at position 1. 13C NMR (151MHz, DMSO) δ -145.33 is carbon 2 on triazole, carbon 3 on 143.58 triazole, carbon 5 on 69.38, carbon 6 on 58.52, carbon 4 on 47.75, and carbon ppm 1 on 39.07. The infrared spectrum peak position is IR (KBr): nu 3147, 1583, 1351, 1193, 1137, 1056, 1015, 790, 740, 664, 643, 617, 571, 514cm-1. Elemental analysis (%): C6H12N4O 4: c35, H5.92, N27.44; test values are: c34.73, H6.21, N27.27, which is not very different from the theoretical values, proved to be of excellent purity.
Example 4
1-vinyl-3-methoxyethyl imidazole dicyandiamide salt
First, bromoethyl methyl ether (30mL, 0.4mol) was weighed out and dissolved in ethyl acetate, the above mixture was added to 1-vinylimidazole (32mL, 0.4mol), heated and stirred at 50 ℃ for 12h, the mixture was cooled to room temperature, washed three times with 70mL ethyl acetate, and after removing the solvent by rotary evaporation, the residual liquid (55.70g, 80%) solidified at room temperature to give 1-vinyl-3-methoxyethyl imidazole bromide salt.
In the second step, silver dicyandiamide (63.94, 0.4mol) is weighed and dissolved in 100mL of deionized water, and 1-vinyl-3-methoxyethyl imidazole bromide (52.218g, 0.3mol) is weighed and dissolved in 100mL of deionized water. Mixing the two solutions in a flask, stirring at 25 deg.C for 24 hr to obtain a white precipitate, filtering, removing solvent by rotary evaporation, dissolving with excessive acetonitrile, precipitating at low temperature, filtering, and rotary evaporating to obtain yellow viscous product (50.02, 95.79%).
Example 5
1-vinyl-3-ethoxyethylimidazole hexafluorophosphate salt
In the first step, chloroethyl ethyl ether (30mL, 0.4mol) was weighed out and dissolved in ethyl acetate, the above mixture was added to 1-vinylimidazole (32mL, 0.4mol), heated at 50 ℃ and stirred for 12h, the mixture was cooled to room temperature, washed three times with 70mL ethyl acetate, and after removing the solvent by rotary evaporation, the residual liquid (67.7g, 90%) was liquid at room temperature to give 1-vinyl-3-ethoxyethylimidazole chloride salt.
In the second step, sodium hexafluorophosphate (67.18g, 0.4mol) is weighed and dissolved in 100mL deionized water, 1-vinyl-3-ethoxyethylimidazole chlorine salt (56.42g, 0.3mol) is weighed and dissolved in 100mL deionized water, the two are mixed and stirred in a flask and stirred at 25 ℃ for 24h, and light yellow oily water-insoluble liquid is generated after the reaction. The liquid was subjected to a liquid separation operation, and water in the ionic liquid was removed by rotary evaporation to obtain a product (80.48g, 90%).
Example 6
1-methyl-3-acetoxyimidazolium borohydride salt
In the first step, ethyl chloroacetate (30mL, 0.4mol) was weighed out and dissolved in ethyl acetate, the mixture was added to 1-methylimidazole (32mL, 0.4mol), heated and stirred at 50 ℃ for 12h, the mixture was cooled to room temperature, washed three times with 70mL of ethyl acetate, and after removing the solvent by rotary evaporation, the residual liquid (65.70g, 80%) solidified at room temperature to give 1-methyl-3-ethyl acetate imidazolium chloride salt.
In the second step, sodium borohydride (15.212, 0.4mol) is weighed and dissolved in 100mL of deionized water, and 1-methyl-3-acetic acid carbethoxy imidazole bromide salt (61.221g, 0.3mol) is weighed and dissolved in 100mL of deionized water. Mixing the two solutions in a flask, stirring at 25 deg.C for 24 hr to obtain a white precipitate, filtering, removing solvent by rotary evaporation, dissolving with excessive acetonitrile, precipitating at low temperature, filtering, and rotary evaporating to obtain a yellow viscous product (52.48, 95%).
Example 7
1-vinyl-3-acetoxyethylimidazolium cyanoboronate
In the first step, ethyl chloroacetate (30mL, 0.4mol) was weighed out and dissolved in ethyl acetate, the above mixture was added to 1-vinylimidazole (32mL, 0.4mol), heated and stirred at 50 ℃ for 12h, the mixture was cooled to room temperature, washed three times with 70mL ethyl acetate, and after removing the solvent by rotary evaporation, the residual liquid (60.70g, 70%) solidified at room temperature to give 1-vinyl-3-acetic acid carbethoxyimidazole chloride salt.
In the second step, sodium cyanoborohydride (138.01, 0.4mol) was weighed out and dissolved in 100mL of deionized water, and 1-vinyl-3-acetoxyimidazolium chloride salt (54.02g, 0.25mol) was weighed out and dissolved in 100mL of deionized water. Mixing the two solutions in a flask, stirring at 25 deg.C for 24h to obtain white precipitate, filtering, removing solvent by rotary evaporation, dissolving with excessive acetonitrile, precipitating at low temperature, filtering, and rotary evaporating to obtain yellow viscous product (37.81, 70%).
Example 8
To further verify the technical results of the present invention, the plasticizers prepared in examples 1 to 3 were added to the epoxy resin curing system in an amount of 4% of the epoxy resin system, and the shore hardness, elongation at break and tensile strength of the propellant after the addition of the plasticizer of the present invention were respectively tested, and the related tests are shown in table 1:
TABLE 1 use effect of ionic liquid plasticizer
| Sample (I) | Shore hardness (D) | Tensile Strength (MPa) | Elongation at Break (%) |
| Blank space | 75 | 15 | 0.68 |
| Example 1 | 71 | 14.5 | 2.93 |
| Example 2 | 72 | 12.5 | 1.45 |
| Example 3 | 73 | 16 | 1.06 |
| Example 4 | 74 | 13.5 | 1.07 |
| Example 5 | 72.5 | 15.5 | 1.33 |
| Example 6 | 74.5 | 13 | 1.17 |
| Example 7 | 71.5 | 15.5 | 1.65 |
As described above, the ionic liquids prepared in examples 1-7 can maintain small changes in tensile strength when added into an epoxy resin system, the elongation at break of the epoxy resin after the ionic liquid prepared in example 1 is increased by 400-.
Example 9
Meanwhile, the ionic liquid plasticizer can also be used in a polyurethane system, and can be used as a plasticizer in the system, so that the elongation at break of the system can be obviously enhanced. The concrete contents are shown in Table 2, and the prepared polyurethane sample is shown in FIG. 1. The polyurethane matrix is prepared by using hydroxyl-terminated polybutadiene (HTPB) as a precursor and 2, 6-Toluene Diisocyanate (TDI) as a curing agent to cure the HTPB.
Table 2: mechanical properties of HTPB and TDI ionic liquid system
| Sample strip | Tensile strength (MPa) | Elongation at Break (%) |
| HTPB + TDI + EXAMPLE 1 | 0.39 | 48.09 |
| HTPB + TDI + EXAMPLE 2 | 0.51 | 64.58 |
| HTPB + TDI + example 3 | 0.52 | 71.38 |
| HTPB + TDI + example 4 | 0.473 | 61.35 |
| HTPB + TDI + example 5 | 0.41 | 51.6 |
| HTPB + TDI + example 6 | 0.47 | 67.5 |
| HTPB + TDI + example 7 | 0.507 | 53.2 |
| Mean value of | 0.469 | 59.67 |
To investigate the interaction between the polyurethane system and the ionic liquid prepared in example 3, the IGM calculation method of Multiwfn software was used. As shown in fig. 2, the value of δ g can measure the interaction between fragments: the larger the value, the stronger the interaction. It is also clear that there is a peak at the position of sign (λ 2) ρ of-0.02 to-0.03 a.u., where the electron density is relatively small. This indicates that there is a strong interaction (non-chemical bond interaction) between the polyurethane system and example 3. The corresponding IGM three-dimensional spatial distribution map is then shown in figure 3, where the colour ranges are the same as in figure 2. The results show that strong interactions exist in the space marked by the arrows, corresponding to hydrogen bond values of-C-h. Thus, the polyurethane system and example 3 form strong hydrogen bonding interactions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An ionic liquid plasticizer, characterized in that the ionic liquid is composed of anions and cations, and the cations of the ionic liquid are any one of the following structures:
the ionic liquid anion is any one of the following structures:
2. the ionic liquid plasticizer according to claim 1, wherein the ionic liquid density is not less than 1.00g cm-1The melting point is lower than-50 ℃.
3. The method for preparing the ionic liquid plasticizer according to claim 1 or 2, comprising the steps of:
(1) adding an imidazole or triazole precursor, a halide RX and a solvent A into a reaction vessel, stirring for reaction, separating liquid after the reaction is finished, washing and extracting to obtain an organic phase, and removing the solvent to obtain an ionic liquid I;
r is
X is a halogen atom;
(2) adding the ionic liquid I obtained in the step (1), inorganic salt and a solvent B into a reaction container for reaction, obtaining a precipitate after the reaction, washing, removing the solvent, and drying to obtain an ionic liquid plasticizer; the anion of the inorganic salt is any one of the following structures, and the cation is Li+Or Ag+，
4. The method for preparing the ionic liquid plasticizer according to claim 3, wherein the molar ratio of the imidazole or triazole to the halide R1 in the step (1) is 1: (1-2).
5. The method for preparing the ionic liquid plasticizer according to claim 3, wherein the reaction temperature in the step (1) is 25-30 ℃ and the reaction time is 12-24 h.
6. The method for preparing an ionic liquid plasticizer according to claim 3, wherein X in the step (1) is Br or Cl.
7. The method for preparing the ionic liquid plasticizer according to claim 3, wherein the molar ratio of the ionic liquid to the inorganic salt in the step (2) is 1 (1-1.4).
8. The method for preparing the ionic liquid plasticizer according to claim 3, wherein the reaction temperature in the step (2) is 25 to 110 ℃ and the reaction time is 12 to 48 hours.
9. The method for preparing the ionic liquid plasticizer according to claim 3, wherein the solvent A is any one of ethyl acetate, acetonitrile or tetrahydrofuran, and the solvent B is deionized water or methanol.
10. The application of the ionic liquid plasticizer according to claim 1 or 2, wherein the ionic liquid plasticizer is applied to the field of polyurethane or epoxy resin, and the addition amount of the ionic liquid plasticizer is 3-8% of the formula mass.
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