CN115557896B - Difunctional imidazole ionic liquid and synthesis method and application thereof - Google Patents
Difunctional imidazole ionic liquid and synthesis method and application thereof Download PDFInfo
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- CN115557896B CN115557896B CN202211205816.9A CN202211205816A CN115557896B CN 115557896 B CN115557896 B CN 115557896B CN 202211205816 A CN202211205816 A CN 202211205816A CN 115557896 B CN115557896 B CN 115557896B
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 56
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229920001721 polyimide Polymers 0.000 claims abstract description 9
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- LEESOPIEUGDJND-UHFFFAOYSA-N 1h-imidazole-4,5-diol Chemical compound OC=1N=CNC=1O LEESOPIEUGDJND-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 229920006264 polyurethane film Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 2
- 239000000178 monomer Substances 0.000 abstract description 26
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000004642 Polyimide Substances 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 150000003949 imides Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 3
- AMSDWLOANMAILF-UHFFFAOYSA-N 2-imidazol-1-ylethanol Chemical compound OCCN1C=CN=C1 AMSDWLOANMAILF-UHFFFAOYSA-N 0.000 description 3
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical compound NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
Classifications
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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
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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
- C07D233/61—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3842—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/3848—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a difunctional imidazole ionic liquid, a synthesis method and application thereof, belonging to the field of novel ionic liquid synthesis, and is characterized in that the structural formula is shown as formula 1: Wherein: r is OH or NH 2;X：Cl、Br、TFSI、SO3 or BF 4; y:1 or 2 or 3; and z:1 or 2 or 3; the novel difunctional imidazole ionic liquid prepared by the invention has adjustable molecular flexibility and reactivity, and the same functional groups at the two ends can be used as reaction monomers for gradual polymerization to be connected into a polymer skeleton, for example, the-OH end capping can react with-NCO to form ionic polyurethane, and the-NH 2 end capping can react with imide to form ionic polyimide.
Description
Technical Field
The invention belongs to the field of novel ionic liquid synthesis, and particularly relates to a difunctional imidazole ionic liquid and a synthesis method and application thereof.
Background
The functional imidazole ionic liquid in the existing scheme is divided into non-functional imidazole ionic liquid, mono-functional imidazole ionic liquid and bi-functional imidazole ionic liquid. The preparation of the non-functionality imidazole ionic liquid is obtained by directly quaternizing N-alkyl imidazole monomer and halohydrocarbon. The monofunctional ionic liquid is prepared by quaternary ammonium substitution reaction of N-alkyl imidazole and functionalized halogenated hydrocarbon or reaction of N-olefin imidazole and halogenated hydrocarbon. The difunctional imidazole ionic liquid is prepared by adopting N-olefine imidazole as a monomer and carrying out quaternization substitution reaction with functionalized halogenated hydrocarbon.
In general, the non-functionality imidazole ionic liquid has the problems of leakage and sealing due to flowability, and can be used as a solvent and a catalyst only; the monofunctional imidazole ionic liquid can be grafted on a macromolecular framework or modified on small molecules through the reaction between functional groups, and can also be synthesized through the free radical polymerization reaction of olefin, so that the problem of leakage of the non-functional imidazole ionic liquid can be solved, but the polymer is not high or the restriction of weak reaction activity due to the steric effect; the difunctional ionic liquid has olefin and reactive functional groups, so that free radical polymerization reaction can be carried out, grafting of the functional groups can be realized, and the design of a reaction system is complex.
Disclosure of Invention
The first aspect of the invention aims to provide a novel difunctional imidazole ionic liquid so as to solve the problem that the existing functional ionic liquid is single in reaction type.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the difunctional imidazole ionic liquid is characterized by having a structural formula shown in formula 1:
Wherein: r is OH or NH 2;
x: cl, br, TFSI, SO 3 or BF 4;
y:1 or 2 or 3;
And z:1 or 2 or 3.
The second aspect of the invention aims to provide a novel preparation method of difunctional imidazole ionic liquid, which is characterized by comprising the following steps:
(1) Dissolving imidazole monomer in anhydrous acetonitrile to prepare 10-50wt% solution for standby, and marking the solution as A solution;
(2) Dissolving a dihalogenated hydrocarbon monomer in anhydrous acetonitrile to prepare a solution with the weight percent of 10-50 percent for standby, and marking the solution as a solution B;
(3) Slowly dropwise adding the solution B into a flask provided with a mechanical stirring, a condensing tube and the solution A for 1-2 h, keeping the reaction temperature at 50-90 ℃ and reacting for 6-96 h under the protection of argon, wherein the molar ratio of imidazole monomer to dihalogenated hydrocarbon monomer is 6-2:1;
(4) Pouring the reaction solution in the step (3) into a precipitator which is 3-5 times larger than the reaction solution to separate out precipitate, and continuously washing the precipitate for three times by using the precipitator;
(5) And (3) dissolving the clean precipitate in the step (4) by using absolute ethyl alcohol, and recrystallizing and purifying at low temperature to obtain the difunctional imidazole ionic liquid.
The reaction equation involved in the invention is as follows:
The further arrangement is that:
in step (1):
The imidazole monomer is selected from any one of 1- (2-hydroxyethyl) imidazole and N- (3-aminopropyl) imidazole;
in the step (2):
The bishalogenated hydrocarbon is selected from any one of 1,2 dichloroethane, 1,2 dibromoethane, 1,4 dichlorobutane or 1,4 dibromobutane.
In the step (3): the reaction temperature is preferably 80 ℃, the reaction time is preferably 48 hours, and the molar ratio of imidazole monomer to dihalohydrocarbon monomer is preferably 2.25:1.
In the step (4):
the precipitant is selected from any one of diethyl ether or ethyl acetate.
The third aspect of the invention aims to provide application of the novel difunctional imidazole ionic liquid in preparation of polyurethane, functional ink, ionic elastomer and ionic polyimide.
The beneficial effects of the invention are as follows:
The key point of the invention is that the No. 1 nitrogen atom on the imidazole ring is functionalized, and the No. 3 nitrogen atom on the imidazole ring is quaternized by using the bishalohydrocarbon, so that the quaternization of the two-molecule functional imidazole is realized. In addition, the number of methylene in the bishalohydrocarbon can be regulated to regulate the flexibility of the difunctional imidazole ionic liquid, and the number of methylene among functional groups and the position regulation reaction activity of the functional groups after the functional groups of the imidazole ring number 1 nitrogen atoms are functionalized can be regulated.
Compared with other technologies, the novel difunctional imidazole ionic liquid prepared by the invention has adjustable molecular flexibility and reactivity, and the same functional groups at two ends can be used as reaction monomers for gradual polymerization to be connected into a polymer skeleton, for example, the-OH end capping can react with-NCO to form ionic polyurethane, and the-NH 2 end capping can react with imide to form ionic polyimide.
The invention is further described below with reference to the drawings and detailed description.
Drawings
FIG. 1 is an H spectrum of a dihydroxyimidazole ionic liquid prepared in example 1;
FIG. 2 is an H-spectrum of the bisaminoimidazole ionic liquid prepared in example 5.
Detailed Description
Example 1: preparation of dihydroxyimidazole ionic liquid
(1) 1- (2-Hydroxyethyl) imidazole monomer is dissolved in anhydrous acetonitrile to prepare a 30wt% solution for standby, and the solution is marked as A solution;
(2) 1,2 dichloroethane monomer is taken and dissolved in anhydrous acetonitrile to prepare a 30wt% solution for standby, and the solution is marked as solution B;
(3) Slowly dropwise adding the solution B into a flask with mechanical stirring, a condenser pipe and the solution A for 2 hours, keeping the reaction temperature at 80 ℃ and reacting for 48 hours under the protection of argon, wherein the molar ratio of the 1- (2-hydroxyethyl) imidazole monomer to the 1, 2-dichloroethane monomer is 2.25:1;
(4) Pouring the reaction solution in the step (3) into ethyl acetate with the volume being more than 3 times of that of the reaction solution to separate out a precipitate, and continuously washing the precipitate with ethyl acetate for three times;
(5) And (3) dissolving the clean precipitate in the step (4) by using absolute ethyl alcohol, recrystallizing and purifying at low temperature to obtain the difunctional imidazole ionic liquid, and measuring the reaction yield to be 89%.
Compound structure confirmation: the H spectrum data of the difunctional imidazole ionic liquid prepared in example 1 is shown in figure 1.
Example 2
The preparation method is the same as in example 1, except that: the reaction temperature of step (3) was varied and its effect on the reaction was tested as shown in table 1:
table 1.
| Sequence number | Reaction temperature (. Degree. C.) | Reaction yield (%) |
| Example 2-1 | 50 | 30 |
| Example 2-2 | 60 | 52 |
| Examples 2 to 3 | 70 | 73 |
| Examples 2 to 4 | 80 | 89 |
| Examples 2 to 5 | 90 | 87 |
Analysis:
As shown in Table 1, when the reaction temperature was low, the yield of the reaction was not high, and as the reaction temperature was increased, the yield was rapidly increased, and the optimum reaction temperature was 80 ℃.
Example 3
The preparation method is the same as in example 1, except that: the reaction time of step (3) was varied and its effect on the reaction was tested as shown in table 2:
Table 2.
| Sequence number | Reaction time | Reaction yield |
| Example 3-1 | 6 | Without any means for |
| Example 3-2 | 10 | 12 |
| Examples 3 to 3 | 24 | 75 |
| Examples 3 to 4 | 48 | 89 |
| Examples 3 to 5 | 72 | 84 |
| Examples 3 to 6 | 96 | 86 |
Analysis:
as shown in Table 2, when the reaction time was low, the yield was almost no, and as the reaction time was increased, the yield was rapidly increased, and the optimal reaction time was 48 hours.
Example 4
The preparation method is the same as in example 1, except that: the molar ratio of imidazole monomer to dihalogenated hydrocarbon monomer reacted in step (3) was varied and its effect on the reaction was tested as shown in table 3:
Table 3.
Analysis:
As shown in Table 3, when the molar ratio of the imidazole monomer to the dihalohydrocarbon monomer was varied, the yield was not affected, but the variation in the molar ratio of the monomers had a large influence on the purity of the product, and when the imidazole monomer was too small or too large, the purity of the product was poor and separation was difficult.
Example 5: preparation of bisaminoimidazole ionic liquid
(1) Dissolving N- (3-aminopropyl) imidazole monomer in anhydrous acetonitrile to prepare a 30wt% solution for standby, and marking the solution as A solution;
(2) Dissolving 1,2 dibromoethane monomer in anhydrous acetonitrile to prepare a 30wt% solution for later use, and marking the solution as a solution B;
(3) Slowly dropwise adding the solution B into a flask provided with a mechanical stirring, a condensing tube and the solution A for 2 hours, keeping the reaction temperature at 80 ℃ and reacting for 48 hours under the protection of argon, wherein the molar ratio of the N- (3-aminopropyl) imidazole monomer to the 1, 2-dibromoethane monomer is 2.25:1;
(4) Pouring the reaction solution in the step (3) into ethyl acetate with the volume being more than 3 times of that of the reaction solution to separate out a precipitate, and continuously washing the precipitate with ethyl acetate for three times;
(5) And (3) dissolving the clean precipitate in the step (4) by using absolute ethyl alcohol, recrystallizing and purifying at low temperature to obtain the amino difunctional imidazole ionic liquid, and measuring the reaction yield to be 88%.
Compound structure confirmation: the H spectrum data of the bisaminoimidazole ionic liquid prepared in example 5 is shown in figure 2.
Application example 1
The polytetrahydrofuran 2000 and the dihydroxyimidazole ionic liquid prepared in the example 1 are dried for 48 hours under vacuum at 60 ℃ to remove water, then are added into a reaction vessel together, wherein the molar ratio of the polytetrahydrofuran 2000 to the dihydroxyimidazole ionic liquid is 2:1, then isophorone diisocyanate and a drop of dibutyltin dilaurate are added, the ratio of NCO to OH is kept at 1.25:1, after the reaction is carried out for 12 hours at 80 ℃, a certain amount of acetone is added to regulate the viscosity during the reaction, the temperature is reduced to 25 ℃, a large amount of acetone is added to prepare a casting solution with 30 percent of solid content, then the casting solution is poured into a mould, and is dried for 6 hours at 60 ℃, and then is dried for 12 hours under vacuum at 80 ℃ to form a film.
And (3) performance detection: the tensile strength of the polyurethane film prepared by the method reaches 3.3Mpa at the tensile rate of 10mm min < -1 >, the elongation at break reaches 313%, and the polyurethane film has the ionic conductivity of 3.6X10 -4S cm-1 because the imidazole ionic liquid is introduced into the molecular structure.
Application example 2
Pyromellitic anhydride and the bisaminoimidazole ionic liquid prepared in example 5 were dried at 60 ℃ for 48 hours under vacuum, water was removed, and then added into a reaction vessel together, wherein the molar ratio of pyromellitic anhydride to bisaminoimidazole ionic liquid was 1.05:1. The dried bisaminoimidazole ionic liquid was dissolved in N 'N-dimethylformamide, and pyromellitic anhydride was also dissolved in N' N-dimethylformamide, to prepare a 30% molar solution. Slowly dropwise adding pyromellitic anhydride solution into the bisaminoimidazole ionic liquid solution at the temperature of 5 ℃ to react for 2 hours to obtain an oligomer solution, pouring the oligomer solution into a mold, and then placing the mold into an oven to carry out high Wen Ya amination. Drying at 80 ℃ for 2 hours, removing redundant solvent, then heating to 120, 160, 200 and 240 ℃ respectively by adopting a step method, maintaining for 1 hour, and finally cooling to room temperature to obtain the ionic polyimide film.
And (3) performance detection: the ionic polyimide film prepared by the method is orange transparent, has tensile strength as high as 15.3Mpa, and has ionic conductivity as well as ionic conductivity of 6.4 multiplied by 10 -4S cm-1 because of the introduction of imidazole ionic liquid into a molecular chain.
Summarizing: the results prove that the novel difunctional imidazole ionic liquid prepared by the invention can be used as a reaction monomer for gradual polymerization to be grafted into a polymer framework, the-OH end cap can be reacted with the-NCO to form ionic polyurethane, and the-NH 2 end cap can be reacted with the imide to form ionic polyimide. The polymer introduced with the imidazole ionic liquid has remarkable improvement on tensile strength and ionic conductivity.
Claims (2)
1. The application of the difunctional imidazole ionic liquid in preparing the polyurethane film is characterized in that: vacuum drying polytetrahydrofuran 2000 and dihydroxyimidazole ionic liquid at 60 ℃ for 48 hours, removing water, then adding the polytetrahydrofuran 2000 and dihydroxyimidazole ionic liquid into a reaction vessel together, wherein the molar ratio of the dihydroxyimidazole ionic liquid to the polytetrahydrofuran 2000 is 2:1, then adding isophorone diisocyanate and dibutyltin dilaurate, keeping the ratio of NCO to OH to be 1.25:1, reacting at 80 ℃ for 12 hours, adding acetone to regulate viscosity during the reaction, reducing the temperature to 25 ℃, adding acetone to prepare casting film liquid with 30% of solid content, pouring the casting film liquid into a mould, drying at 60 ℃ for 6 hours, and then vacuum drying at 80 ℃ for 12 hours to form a film;
The tensile strength of the polyurethane film prepared by the method reaches 3.3Mpa under the tensile rate of 10mm min- 1, the elongation at break reaches 313%, and the ionic conductivity is 3.6X10 -4S cm-1;
The structural formula of the dihydroxyimidazole ionic liquid is shown as follows:
2. The application of the difunctional imidazole ionic liquid in preparing the ionic polyimide film is characterized in that: vacuum drying pyromellitic anhydride and bisaminoimidazole ionic liquid at 60 ℃ for 48 hours, removing water, then adding the pyromellitic anhydride and the bisaminoimidazole ionic liquid into a reaction container, wherein the molar ratio of the pyromellitic anhydride to the bisaminoimidazole ionic liquid is 1.05:1, dissolving the dried bisaminoimidazole ionic liquid into N 'N-dimethylformamide, dissolving the pyromellitic anhydride into the N' N-dimethylformamide as well, preparing a solution with the molar concentration of 30%, slowly dropwise adding the pyromellitic anhydride solution into the bisaminoimidazole ionic liquid solution at 5 ℃, reacting for 2 hours to obtain an oligomer solution, pouring the oligomer solution into a mold, then placing the oligomer solution into an oven for amination with high Wen Ya, firstly drying at 80 ℃ for 2 hours, removing redundant solvents, then heating by a step method, respectively heating to 120, 160, 200 and 240 ℃ and keeping the temperature for 1 hour, and finally cooling to room temperature to obtain the ionic polyimide film;
the ionic polyimide film prepared by the method has the tensile strength of 15.3Mpa and the ionic conductivity of 6.4 multiplied by 10 -4S cm-1;
the structural formula of the bisaminoimidazole ionic liquid is shown as follows:
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