CN103965111A - Gemini quaternary ammonium salt containing salicylaldehyde Schiff base and preparation method thereof - Google Patents
Gemini quaternary ammonium salt containing salicylaldehyde Schiff base and preparation method thereof Download PDFInfo
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- C07D233/61—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 nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
The invention provides a gemini quaternary ammonium salt containing salicylaldehyde Schiff base. Combined with the structural characteristics of Schiff base liquid crystal molecules and quarternary ammonium ion liquid crystal molecules, according to the needs and technical requirements of liquid crystal application, salicylaldehyde Schiff base imine (-CH=N-) is taken as a bridged bond for connecting conjugated mesogenic units to form functional ion liquid crystal with visible light response; besides, quarternary ammonium cations are associated with phenoxyl anions of the salicylaldehyde Schiff base imine to form an inner salt structure of the quarternary ammonium cations and the phenoxyl anions of the salicylaldehyde Schiff base imine; the melting point of the inner salt structure is reduced to form a stable liquid crystal phase with wider range of temperature, and potential wide application in the fields of optical information storage, light control molecular orientation, molecular switch, integrated optics and the like are developed.
Description
Technical field
The present invention relates to quaternary ammonium salt, particularly a kind of gemini quaternary ammonium salt that contains schiff base of salicylaldehyde, belongs to organic fine chemical field.
Technical background
In liquid crystal molecule structure, introduce ion unit, be called as ion liquid crystal (ionic liquid crystals ILCs).By coulomb reactive force, intermolecular interaction can strengthen mesomorphous phase time, improves its interface performance.Have been found that quaternary ammonium ion liquid crystal material has mostly shown smectic phase in very wide temperature range.Ion liquid crystal not only retains the premium properties of former liquid crystal, has very low vapour pressure.Can be by selecting quaternary phosphine cation group, or the anionic group such as carboxylic acid, sulfonic acid, and the suitably change of negative and positive counter ion, make its liquid crystal property that many variations occur, as mesomorphous phase temperature raises, mesomorphous phase temperature range broadens, and liquid crystal texture changes, and the responsivenesss such as optical, electrical magnetic is obviously strengthened etc.
Much research finds that the imines (C=N-) in Schiff's base molecular structure can be used as the bridged bond of conjugation aromatic ring mesomorphic unit, significant on formation liquid crystal molecule wire conjugation rigid element; Phenolic hydroxyl group in schiff base of salicylaldehyde (CH=N-) molecular structure is also a kind of motivating force of Liquid Crystal Molecules Alignment ordered orientation; Schiff base of salicylaldehyde is again a kind of chelating ligand, can selectivity and heavy metal ion carry out complex reaction, make complexes liquid crystal material of all kinds.
Given this, the invention provides a kind of gemini quaternary ammonium salt that contains schiff base of salicylaldehyde, it is the constructional feature in conjunction with Schiff's base liquid crystal molecule and quaternary ammonium ion liquid crystal molecule, need and technical requirements according to liquid crystal applications, carry out molecular designing, the key bridge connecting schiff base of salicylaldehyde imines (CH=N-) as conjugation mesomorphic unit, forms the functional ionic liquid crystal with visible light-responded property; Simultaneously that quaternary ammonium cation is associated with the phenol oxygen anion of schiff base of salicylaldehyde imines, form the inner salt structure of quaternary ammonium cation-schiff base of salicylaldehyde phenol oxygen base negatively charged ion, reduce its fusing point, the stable liquid crystalline phase of the wider model of formation temperature, excavates its potential wide application in the fields such as optical information storage, light-operated molecular orientation, molecular switch, integrated optics.
Summary of the invention
The invention provides a kind of gemini quaternary ammonium salt that contains schiff base of salicylaldehyde, there is structure shown in general formula (Ia) or general formula (Ib):
Q in its formula of (Ia) or general formula (Ib) is selected from C
1～C
20a kind of in alkylene or do not choose any, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -cH
3cOO
-, CF
3cOO
-, BF
4 -, PF
6 -, SbF
6 -, CF
3sO
3 -, C
4f
9sO
3 -or (CF
3sO
2)
2n
-in one, Ar is selected from structure shown in general formula (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe):
R in its formula of (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe) is selected from H, F, Cl, Br, CN, NO
2, OH, COOH, C
1～C
20alkyl, C
1～C
20-oxyl, C
1～C
20sulfenyl or two (C
1～C
20alkyl) one or more in amido, n is selected from the one in 1,2 or 3, and Y is selected from the one in O, S or NH.
Shown in general formula provided by the invention (Ia) or general formula (Ib), the schiff base of salicylaldehyde gemini quaternary ammonium salt that contains of structure is prepared according to following synthesis step:
The preparation of step 1 bigcatkin willow hydroformylation gemini quaternary ammonium salt
Reaction formula:
Operation steps: take general formula (IIIa) or general formula (IIIb) and 5-chloromethyl salicylaldehyde and be dissolved in respectively in solvent, make general formula (IIIa) or general formula (IIIb) solution and 5-chloromethyl salicylaldehyde solution; Control described general formula (IIIa) or general formula (IIIb) solution temperature to 0～60 DEG C, under stirring, slowly 5-chloromethyl salicylaldehyde solution is joined in general formula (IIIa) or general formula (IIIb) solution, react 2～6 hours, after this distilling off solvent residuum, with dehydrated alcohol, described residue is dissolved to recrystallize and purify, make the bigcatkin willow hydroformylation gemini quaternary ammonium salt of structure shown in general formula (IVa) or general formula (IVb).
Its formula of (IIIa) or general formula (IIIb) be selected from as reaction formula 1. as shown in structure, the Q of reaction formula in is 1. selected from C
1～C
20a kind of in alkylene or do not choose any;
Described solvent refers to acetone, butanone, 1,4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, chlorobenzene, ethyl acetate, methyl acetate, butylacetate, chloroform, tetracol phenixin, 1,2-ethylene dichloride, methylcyclohexane, N, one or more in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or acetonitrile;
The molar weight ratio of described general formula (IIIa) or general formula (IIIb) and 5-chloromethyl salicylaldehyde is 1: 2.0～2.5;
Described solvent load is general formula (IIIa) or general formula (IIIb) and 5-chloromethyl salicylaldehyde quality summation 2～10 times.
The preparation of the gemini quaternary ammonium salt that step 2 contains schiff base of salicylaldehyde
Reaction formula:
Operation steps: take respectively general formula (IVa) or general formula (IVb) bigcatkin willow hydroformylation gemini quaternary ammonium salt and Ar-NH
2be dissolved in organic solvent, Glacial acetic acid is as souring agent and catalyzer, after back flow reaction 4～12 hours, steam the azeotrope of organic solvent and water, after thin layer chromatography detection condensation reaction finishes, cooling reaction product system temperature is to room temperature, add MX solution, stir and complete after replacement(metathesis)reaction for 2～4 hours, filter and remove insoluble substance, gained filtrate is concentrated, make the gemini quaternary ammonium salt that contains schiff base of salicylaldehyde of structure shown in general formula (Ia) or general formula (Ib).
Wherein the Q of reaction formula in is 2. selected from C
1～C
20a kind of in alkylene or do not choose any, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, CH
3cOO
-, CF
3cOO
-, BF
4 -, PF
6 -, SbF
6 -, CF
3sO
3 -, C
4f
9sO
3 -or (CF
3sO
2)
2n
-in one, Ar is selected from structure shown in general formula (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe):
R in its formula of (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe) is selected from H, F, Cl, Br, CN, NO
2, OH, COOH, C
1～C
20alkyl, C
1～C
20-oxyl, C
1～C
20sulfenyl or two (C
1～C
20alkyl) one or more in amido, n is selected from the one in 1,2 or 3, and Y is selected from the one in O, S or NH.
Described Ar-NH
2be selected from structure shown in general formula (IIa-a), general formula (IIb-b), general formula (IIc-c), general formula (IId-d) or general formula (IIe-e):
R in its formula of (IIa-a), general formula (IIb-b), general formula (IIc-c), general formula (IId-d) or general formula (IIe-e) is selected from H, F, Cl, Br, CN, NO
2, OH, COOH, C
1～C
20alkyl, C
1～C
20-oxyl, C
1～C
20sulfenyl or two (C
1～C
20alkyl) one or more in amido, n is selected from the one in 1,2 or 3, and Y is selected from the one in O, S or NH;
M in described MX is selected from K or Na, and the X in MX is selected from F, Cl, Br, NO
3, HSO
4, CH
3cOO, C
3f
7cOO, BF
4, PF
6, SbF
6, CF
3sO
3, C
4f
9sO
3or (CF
3sO
2)
2one in N.
Described organic solvent refers to one or more in methyl alcohol, ethanol, propyl alcohol, acetone, butanone, DMF, N,N-dimethylacetamide, methyl-sulphoxide or acetonitrile.
Described general formula (IVa) or general formula (IVb) bigcatkin willow hydroformylation gemini quaternary ammonium salt and Ar-NH
2molar weight ratio be 1: 2.0～2.5.
The consumption of described organic solvent is general formula (IVa) or general formula (IVb) bigcatkin willow hydroformylation gemini quaternary ammonium salt and Ar-NH
22～10 times of quality summation.
Specific embodiment
By embodiment below, the gemini quaternary ammonium salt that contains schiff base of salicylaldehyde and the preparation method of structure shown in general formula provided by the invention (Ia) or general formula (Ib) are further illustrated, its object is to understand better content of the present invention.Therefore, the gemini quaternary ammonium salt and the preparation method that in embodiment, shown in unlisted general formula (Ia) or general formula (Ib), contain schiff base of salicylaldehyde, should not be considered as limiting the scope of the invention.
The preparation of the Neo Heliopan AP (Ia-1) that embodiment 1 contains schiff base of salicylaldehyde
The preparation of step 1 bigcatkin willow hydroformylation Shuangzi imidazole salts IVa-1
In the four-hole boiling flask that agitator is housed, take 1,20 grams of two (1-imidazolyl) butane of 4-are dissolved in 110 milliliters of Isosorbide-5-Nitrae-dioxane, make 1,1 of two (1-imidazolyl) butane of 4-, 4-dioxane solution, then take 40 grams of 5-chloromethyl salicylaldehydes and be dissolved in 80 milliliters of Isosorbide-5-Nitrae-dioxane, make the Isosorbide-5-Nitrae of 5-chloromethyl salicylaldehyde
-dioxane solution.Control 5, 1 of chloromethyl salicylaldehyde, 4-dioxane solution temperature is between 8～15 DEG C, under stirring by 1, 1 of two (1-imidazolyl) butane of 4-, 4-dioxane solution slowly adds 1 of 5-chloromethyl salicylaldehyde, in 4-dioxane solution, react after 4 hours, temperature is brought up to 50～55 DEG C, stirring reaction 10 hours again, reaction product system temperature is down to 5～10 DEG C, filter, filter cake uses ethyl alcohol recrystallization, after dry, make the bigcatkin willow hydroformylation Neo Heliopan AP (IVa-1) of 45 grams of light yellow crystal shapes, yield 83.3%, fusing point test 76-77 DEG C.
Ultimate analysis: C
26h
28cl
2n
4o
4measured value (calculated value): C58.66 (58.76), H5.30 (5.31), N10.43 (10.54), Cl13.32 (13.34).
IR spectrum (KBr compressing tablet, cm
-1): 3413,2907,2833,2714,1706,1616,1548,1278.
H
1-NMR composes (DMSO-d
6, 8): 1.75 (m, 4H), 3.65 (t, 4H), 4.65 (s, 4H), 6.54～7.27 (m, 12H), 10.24 (s, 2H), 11.35 (s, 2H).
The preparation of the Neo Heliopan AP (Ia-1) that step 2 contains schiff base of salicylaldehyde
Take 10 grams of bigcatkin willow hydroformylation Neo Heliopan APs (IVa-1) and 11.5 grams of 4-dodecyl aniline are dissolved in 80 milliliters of ethanol, 0.2 milliliter of Glacial acetic acid is as catalyzer, back flow reaction 8 hours, component distillation part ethanol, promotes condensation reaction to carry through to the end.After reaction finishes, deep cooling reaction product system temperature, to room temperature, filters, and isopropylcarbinol recrystallization is dried and makes the Neo Heliopan AP (Ia-1) that yellow contains schiff base of salicylaldehyde.
Ultimate analysis: C
62h
86cl
2n
6o
2measured value (calculated value): C72.88 (73.13), H8.47 (8.51), N8.25 (8.25), Cl6.83 (6.96).
IR spectrum (KBr compressing tablet, cm
-1): 3402,2928,2837,1687,1617,1564,1318,1108.
H
1-NMR(DMSO-d
6，)：1.02(t，6H)，1.29～1.76(m，44H)，2.78(t，4H)，3.77(s，4H)，4.39(s，4H)，6.74～7.45(m，20H)，8.41(s，2H)，13.36(s，2H)。
Dsc analysis data:
Wherein Cr represents crystallization phases, and SmX or SmA represent smectic X phase or smectic A phase, and ISO is isotropic phase, the digitized representation transformation temperature of bracket outside (DEG C), the digitized representation enthalpy change (kJ/mol) in bracket.There is smectic phase feature from the known Shuangzi imidazole salts (Ia-1) that contains schiff base of salicylaldehyde of dsc analysis data of Ia-1.
The preparation of the Neo Heliopan AP (Ia-2) that embodiment 2 contains schiff base of salicylaldehyde
According to preparation method and the step of embodiment 1, by 1 of step 1 in embodiment 1, it is 1 that two (1-imidazolyl) butane of 4-change, two (1-imidazolyl methyl) benzene of 4-, can make the bisque Neo Heliopan AP that contains schiff base of salicylaldehyde (Ia-2), according to the method for embodiment 1, by fusing point test, IR spectroscopic analysis and H
1the chemical structure of-NMR analysis confirmation Ia-2 meets shown in Ia-2 structural formula.
Dsc analysis data:
Wherein Cr represents crystallization phases, and SmX or SmA represent smectic X phase or smectic A phase, and ISO is isotropic phase, bracket outside digitized representation transformation temperature (DEG C), the digitized representation enthalpy change (kJ/mol) in bracket.There is smectic liquid crystal feature from known its of dsc analysis data of (1a-2).
The preparation of the bipyridine salt (Ib-1) that embodiment 3 contains schiff base of salicylaldehyde
According to preparation method and the step of embodiment 1, the Isosorbide-5-Nitrae of step 1 in embodiment 1-bis-(1-imidazolyl) butane is changed as 4,4'-Bipyridine, prepare the light yellow bipyridine salt that contains schiff base of salicylaldehyde (Ib-1):
According to the method for embodiment 1, by fusing point test, IR spectroscopic analysis and H
1the chemical structure of the bipyridine salt (Ib-1) that-NMR analysis confirmation contains schiff base of salicylaldehyde meets shown in Ib-1 structural formula, and the dsc analysis data of Ib-1 are:
Dsc analysis data show that Ib-1 has smectic A phase liquid crystal feature.
The preparation of the bipyridine salt (Ib-2) that embodiment 4 contains schiff base of salicylaldehyde
According to preparation method and the step of embodiment 1, by 1 of step 1 in embodiment 1, it is 4 that two (1-imidazolyl) butane of 4-change, 4 '-bipyridine, in embodiment 1, the 4-dodecyl aniline of step 2 changes as p-Nitroaniline, make the bolarious bipyridine salt that contains schiff base of salicylaldehyde (Ib-2), fusing point: thermolysis.According to the method for embodiment 1, by fusing point test, IR spectroscopic analysis and H
1the chemical structure of the bipyridine salt (Ib-2) that-NMR analysis confirmation contains schiff base of salicylaldehyde meets shown in Ib-2 structural formula, and dsc analysis data show that Ib-2 does not have liquid crystal phase.
Get 2 grams of Ib-2 thermosols in 50 milliliters of ethanol, regulate pH～9.0 with alcohol sodium alcohol solution, then slowly add in neutralized verdigris ethanolic soln, solution colour becomes brown gradually by redness, separates out khaki color solid complexes after a few days.
Get 2 grams of Ib-2 thermosols in 50 milliliters of ethanol, and add saturated Potassium Hexafluorophosphate ethanolic soln, in stirring, slowly separate out solid, filter and remove described solid, filtrate is concentrated, make thick brown (Ib-2-1), the structural formula of Ib-2-1 is as follows:
The preparation of the bipyridine salt (Ib-3) that embodiment 5 contains schiff base of salicylaldehyde
According to preparation method and the step of embodiment 1, by 1 of step 1 in embodiment 1, it is 4 that two (1-imidazolyl) butane of 4-change, 4 '-bipyridine, in embodiment 1, the 4-dodecyl aniline of step 2 changes as 4-n-dodecane oxygen base aniline, can make the flaxen bipyridine salt that contains schiff base of salicylaldehyde (Ib-3), according to the method for embodiment 1, by fusing point test, IR spectroscopic analysis and H
1the chemical structure of the bipyridine salt (Ib-3) that-NMR analysis confirmation contains schiff base of salicylaldehyde meets shown in Ib-3 structural formula.The dsc analysis data of Ib-3:
Wherein Cr represents crystallization phases, and SmA represents smectic A phase, and ISO is isotropic phase, the digitized representation transformation temperature of bracket outside (DEG C), the digitized representation enthalpy change (kJ/mol) in bracket.There is smectic liquid crystal feature from the known Shuangzi imidazole salts (Ib-3) that contains schiff base of salicylaldehyde of dsc analysis data of Ib-3.
The preparation of the double amidopyridine salt (Ib-4) that embodiment 6 contains schiff base of salicylaldehyde
According to preparation method and the step of embodiment 1, by 1 of step 1 in embodiment 1, it is 4 that two (1-imidazolyl) butane of 4-change, 4 '-bipyridine, 4-dodecyl aniline in step 2 changes as 2-amino-6-methoxybenzothiazole, make the bipyridine salt that contains schiff base of salicylaldehyde (Ib-4) of orange, according to the method for embodiment 1, by fusing point test, IR spectroscopic analysis and H
1the chemical structure of the bipyridine salt (Ib-4) that-NMR analysis confirmation contains schiff base of salicylaldehyde meets shown in Ib-4 structural formula.(Ib-4) fusing point: thermolysis, dsc analysis data show that Ib-4 does not have liquid crystal phase.
Claims (2)
1. contain a gemini quaternary ammonium salt for schiff base of salicylaldehyde, there is structure shown in general formula (Ia) or general formula (Ib):
Q in its formula of (Ia) or general formula (Ib) is selected from C
1～C
20a kind of in alkylene or do not choose any, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, CH
3cOO
-, CF
3cOO
-, BF
4 -, PF
6 -, SbF
6 -, CF
3sO
3 -, C
4f
9sO
3 -or (CF
3sO
2)
2n
-in one, Ar is selected from structure shown in general formula (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe):
R in its formula of (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe) is selected from H, F, Cl, Br, CN, NO
2, OH, COOH, C
1～C
20alkyl, C
1～C
20-oxyl, C
1～C
20sulfenyl or two (C
1～C
20alkyl) one or more in amido, n is selected from the one in 1,2 or 3, and Y is selected from the one in O, S or NH.
2. according to the preparation method of gemini quaternary ammonium salt who contains schiff base of salicylaldehyde described in claim 1, it is characterized in that realizing according to following preparation process:
The preparation of step 1 bigcatkin willow hydroformylation gemini quaternary ammonium salt
Reaction formula:
Operation steps: take general formula (IIIa) or general formula (IIIb) and 5-chloromethyl salicylaldehyde and be dissolved in respectively in solvent, make general formula (IIIa) or general formula (IIIb) solution and 5-chloromethyl salicylaldehyde solution; Control described general formula (IIIa) or general formula (IIIb) solution temperature to 0～60 DEG C, under stirring, 5-chloromethyl salicylaldehyde solution is joined in general formula (IIIa) or general formula (IIIb) solution, react after 2～6 hours, distilling off solvent residuum, with dehydrated alcohol, described residue is dissolved to recrystallize and purify, make the bigcatkin willow hydroformylation gemini quaternary ammonium salt of structure shown in general formula (IVa) or general formula (IVb);
Its formula of (IIIa) or general formula (IIIb) be selected from as reaction formula 1. as shown in structure, the Q of reaction formula in is 1. selected from C
1～C
20a kind of in alkylene or do not choose any;
Described solvent refers to acetone, butanone, 1,4-dioxane, tetrahydrofuran (THF), glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, chlorobenzene, ethyl acetate, methyl acetate, butylacetate, chloroform, tetracol phenixin, 1,2-ethylene dichloride, methylcyclohexane, N, one or more in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or acetonitrile;
The molar weight ratio of described general formula (IIIa) or general formula (IIIb) and 5-chloromethyl salicylaldehyde is 1: 2.0～2.5;
Described solvent load is general formula (IIIa) or general formula (IIIb) and 5-chloromethyl salicylaldehyde quality summation 2～10 times;
The preparation of the gemini quaternary ammonium salt that step 2 contains schiff base of salicylaldehyde
Reaction formula:
Operation steps: take respectively general formula (IVa) or general formula (IVb) bigcatkin willow hydroformylation gemini quaternary ammonium salt and Ar-NH
2be dissolved in organic solvent, Glacial acetic acid is as souring agent and catalyzer, after back flow reaction 4～12 hours, steam the azeotrope of organic solvent and water, after thin layer chromatography detection condensation reaction finishes, cooling reaction product system temperature is to room temperature, add MX solution, stir and complete after replacement(metathesis)reaction for 2～4 hours, filter and remove insoluble substance, gained filtrate is concentrated, make the gemini quaternary ammonium salt that contains schiff base of salicylaldehyde of structure shown in general formula (Ia) or general formula (Ib);
Wherein the Q of reaction formula in is 2. selected from C
1～C
20a kind of in alkylene or do not choose any, X
-be selected from F
-, Cl
-, Br
-, NO
3 -, HSO
4 -, CH
3cOO
-, CF
3cOO
-, BF
4 -, PF
6 -, SbF
6 -, CF
3sO
3 -, C
4f
9sO
3 -or (CF
3sO
2)
2n
-in one, Ar is selected from structure shown in general formula (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe):
R in its formula of (IIa), general formula (IIb), general formula (IIc), general formula (IId) or general formula (IIe) is selected from H, F, Cl, Br, CN, NO
2, OH, COOH, C
1～C
20alkyl, C
1～C
20-oxyl, C
1～C
20sulfenyl or two (C
1～C
20alkyl) one or more in amido, n is selected from the one in 1,2 or 3, and Y is selected from the one in O, S or NH;
Described Ar-NH
2be selected from structure shown in general formula (IIa-a), general formula (IIb-b), general formula (IIc-c), general formula (IId-d) or general formula (IIe-e):
R in its formula of (IIa-a), general formula (IIb-b), general formula (IIc-c), general formula (IId-d) or general formula (IIe-e) is selected from H, F, Cl, Br, CN, NO
2, OH, COOH, C
1～C
20alkyl, C
1～C
20-oxyl, C
1～C
20sulfenyl or two (C
1～C
20alkyl) one or more in amido, n is selected from the one in 1,2 or 3, and Y is selected from the one in O, S or NH;
M in described MX is selected from K or Na, and the X in MX is selected from F, Cl, Br, NO
3, HSO
4, CH
3cOO, C
3f
7cOO, BF
4, PF
6, SbF
6, CF
3sO
3, C
4f
9sO
3or (CF
3sO
2)
2one in N;
Described organic solvent refers to methyl alcohol, ethanol, propyl alcohol, acetone, butanone, N, dinethylformamide, N, one or more in N-N,N-DIMETHYLACETAMIDE, methyl-sulphoxide or acetonitrile, described consumption of organic solvent is general formula (IVa) or general formula (IVb) bigcatkin willow hydroformylation gemini quaternary ammonium salt and Ar-NH
22～10 times of quality summation;
Described general formula (IVa) or general formula (IVb) bigcatkin willow hydroformylation gemini quaternary ammonium salt and Ar-NH
2molar weight ratio be 1: 2.0～2.5.
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| CN104356052A (en) * | 2014-10-14 | 2015-02-18 | 淮海工学院 | Cross-linkable copper (II) monomer containing quaternary ammonium cation and salicylic Schiff base and preparation method of cross-linkable copper (II) |
| CN114602557A (en) * | 2022-03-23 | 2022-06-10 | 国科广化精细化工孵化器(南雄)有限公司 | Imidazoline modified cobalt metal catalyst and preparation method and application thereof |
| CN116239504A (en) * | 2023-03-06 | 2023-06-09 | 江苏海洋大学 | Isocyanate crosslinking agent containing double quaternary ammonium cations and polysulphonazole and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104356052A (en) * | 2014-10-14 | 2015-02-18 | 淮海工学院 | Cross-linkable copper (II) monomer containing quaternary ammonium cation and salicylic Schiff base and preparation method of cross-linkable copper (II) |
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| CN116239504A (en) * | 2023-03-06 | 2023-06-09 | 江苏海洋大学 | Isocyanate crosslinking agent containing double quaternary ammonium cations and polysulphonazole and preparation method thereof |
| CN116239504B (en) * | 2023-03-06 | 2023-11-17 | 江苏海洋大学 | Isocyanate crosslinking agent containing double quaternary ammonium cations and polysulphonazole and preparation method thereof |
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