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Szpecht, Andrea ; Zielinski, Dawid ; Roszyk, Szymon , et al. Molecules,2024,29(19):4538. DOI: 10.3390/molecules29194538
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Abstract: This study focuses on the synthesis, characterization, and application of four ionic liquids (ILs), three of which are being reported for the first time, with unique thermal properties and diverse anion-cation combinations, specifically in the context of epoxy resin polymerization. 1-3-Didodecylimidazolium dicyanamide (dDDIM DCA), 1-3-Didodecylimidazolium docusate (dDDIM DOSS), 1-ethyl-3-methylimidazolium dicyanamide, and 1-ethyl-3-methylimidazolium docusate (EMIM DOSS) were used to prepare six different mixtures with the same cation and with varying concentrations of DCA components, which is the main factor of an efficient polymerization, while the other component is intended to modify the properties of the cured resin. Mixtures based on EMIM cation demonstrated increased enthalpy and lower onset polymerization temperatures, indicating more efficient curing processes. The hardness of cured epoxy resins can be adjusted by altering the curing temperature and IL composition, with EMIM DCA and EMIM DOSS mixtures displaying high Shore A hardness, suitable for durable surface applications. In contrast, mixtures with higher dDDIM DCA proportions offered a balance between rigidity and flexibility, ideal for applications requiring both mechanical strength and elasticity
Keywords: ionic liquids ; epoxy resin ; crosslinking
CAS No. : | 1934-75-4 | MDL No. : | MFCD00003535 |
Formula : | C2N3Na | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | IXBPPZBJIFNGJJ-UHFFFAOYSA-N |
M.W : | 89.03 | Pubchem ID : | 4350929 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P264-P270-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P330-P362-P403+P233-P501 | UN#: | |
Hazard Statements: | H302+H312+H332-H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; In N,N-dimethyl-formamide; xylene; at 80 - 85℃; for 7h; | Reference Example 1 N1-octyl-N1-methyl-cyanoguanidine; Under ice-cooling, to a suspension of N-methyloctylamine (35.0 g, 0.24 mol) and sodium dicyanamide (26.1 g, 0.29 mol) in xylene (320 ml) and DMF (80 ml) was added concentrated sulfuric acid (12.1 g), and the mixture was stirred for 7 hr with heating at 80-85°C. Under ice-cooling, water was added, and the precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to give colorless crystals (21.6 g) with melting point of 101 to 104°C. Further, the xylene layer was washed with water, dried over anhydrous magnesium sulfate, concentrated and cooled. The precipitated crystals were collected by filtration to give the title compound (17.1 g) as colorless crystals. 1H-NMR(DMSO-d6) delta: 0.86 (3H, t, J=6Hz,CH3), 1.1-1.5 (12H, m, (CH2)6), 2.85 (3H, s, CH3NCH2), 3.24 (2H, t, J=7Hz, CH3NCH2), 6.91(2H, s, NH.x.2). |
Yield | Reaction Conditions | Operation in experiment |
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In 5,5-dimethyl-1,3-cyclohexadiene; for 12h;Reflux; | For representative unsymmetrical analogues (e.g. JD005, JD007): A mixture of sodium dicyanamide (1.335g, 0.015 mol) and <strong>[25150-61-2]pyrrolidine hydrochloride</strong> or dimethylamine hydrochloride (0.015 mol) in xylenes (40 mL) was refluxed for 12 h. After it was cooled to room temperature, the reaction mixture was evaporated to dryness under reduced pressure. The residue was crystallized from methanol to obtain the pure N-cyanopyrrolidine-1- carboximidamide and 3-cyano-l,l-dimethylguanidine products. Then these cyanoguanidines (0.015 mol) were dissolved separately in xylenes (40 mL) and piperidine hydrochloride or morpholine hydrochloride (0.015 mol) was added. The mixture was refluxed for 48 h, the solvent was removed under vacuum and the residue was recrystallized twice from methanol to obtain the two unsymmetrical analogues, JD005 and JD007, respectively.; The title compound, JD005, was obtained by following general procedure C using first <strong>[25150-61-2]pyrrolidine hydrochloride</strong> and then piperidine hydrochloride in 35% yield after crystallization from methanol. 1H NMR (300 MHz, DMSO-d6): δ 6.88 (IH, s), 3.40 (4H, br s), 3.29 (4H, br s), 1.83 (4H, br s), 1.54 (2H, br s), 1.48 (4H, br s). 13C NMR (75 MHz, DMSO-d6): δ 156.4, 156.1, 46.9, 45.6, 25.1, 24.8, 23.7. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | General procedure: A mixture of sodium dicyanoamide (1.335 g, 0.015 mol) and <strong>[25150-61-2]pyrrolidine hydrochloride</strong> or dimethylamine hydrochloride (0.015 mol) in xylenes (40 mL) was refluxed for 12 h. After it was cooled to 21 C, the reaction mixture was evaporated to dryness under reduced pressure. The residue was crystallized from MeOH to get the pure alkyldicyandiamide product as an intermediate. The alkyldicyandiamide (0.015 mol) was then dissolved in xylenes (40 mL), and then either piperidine hydrochloride or morpholine hydrochloride (0.015 mol) was added and the mixture was refluxed for another 48 h. The solvent was removed under vacuum and the crude residue was recrystallized twice from MeOH to provide the desired product 005. |