CN101255226B - Ionic liquid polymer containing imidazole in main chain and method for synthesizing same - Google Patents
Ionic liquid polymer containing imidazole in main chain and method for synthesizing same Download PDFInfo
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- CN101255226B CN101255226B CN2008100178225A CN200810017822A CN101255226B CN 101255226 B CN101255226 B CN 101255226B CN 2008100178225 A CN2008100178225 A CN 2008100178225A CN 200810017822 A CN200810017822 A CN 200810017822A CN 101255226 B CN101255226 B CN 101255226B
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Abstract
The invention provides a synthetic method of ionic liquid polymer containing imidazole in main chain, comprising imidazole respectively reacting with 2-chlorohydrin and methyl chloroacetate to synthesize chloridized 1,3- bi(2-hydroxyethyl)imidazole ionic liquid and chloridized 1,3- bi(2-methoxy-2-oxyethyl)imidazole ionic liquid; the two ionic liquid being used as monomer to perform melt phase polycondensation in the present of catalyst SnCl2. The ionic liquid polymer has good conductivity property (conductivity: 5.4-7.2*10-5S/m.). Because the ionic liquid unit is induced, the new type polymer has application future in polyelectrolyte, gas separation film and so on.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to ion liquid polymer and compound method thereof that one type of novel symmetric function is rolled into a ball, relate in particular to ion liquid polymer and compound method thereof that a kind of main chain contains imidazoles.
Background technology
Ionic liquid is as a kind of green solvent and catalyzer since have non-volatile, do not burn, almost do not have vp, be heated and can not expand, characteristics such as good conductivity are widely used in fields such as electrochemistry, organic synthesis, catalysis and extracting and separating.In the last few years, the application of ionic liquid in field of polymer technology also more and more came into one's own, and it is significant to the exploitation new functional macromolecule material that the characteristic that ionic liquid had is combined with macromolecular material.Contain the polymkeric substance of ionic liquid structure owing to have good electrical conductivity, wide application prospect is arranged aspect solid electrolyte.At present, containing ion liquid polymkeric substance mainly is the polymkeric substance of suspension ionic liquid structure on the side chain, is the macrogol ester of methylacrylic acid like monomer, is to be connected with imidazole ion liquid at the polyoxyethylene glycol the other end; Monomer is the alkyl ester of methylacrylic acid, is connected with imidazole ion liquid at the other end of alkyl ester; With chlorination 1-vinyl-3-ethyl imidazol(e) ionic liquid, chlorination 1-vinyl-2-normal-butyl imidazole ion liquid is monomer, obtains polymkeric substance that contains on the side chain by the imidazole ion liquid type or the like, and this type of ion liquid polymer all has certain electroconductibility.But, on main chain, contain ion liquid polymer of imidazoles and preparation method thereof, do not appear in the newspapers as yet at present.
Summary of the invention
The purpose of this invention is to provide the ion liquid polymer that contains imidazoles on a kind of main chain.
Another object of the present invention provides the compound method that a kind of main chain contains the ion liquid polymer of imidazoles.
One, the ion liquid polymer that contains imidazoles on the main chain
The ion liquid polymer that contains imidazoles on the main chain of the present invention, its chemical structural formula is following:
N=9～20, the molecular weight of polymkeric substance are 3700～8100.
Two, contain the preparation of the ion liquid polymer of imidazoles on the main chain
The preparation method of ion liquid polymer of the present invention; Be earlier with imidazoles respectively with methyl chloroacetate, ethylene chlorhydrin synthesizing chlorinated 1; 3-two (2-hydroxyethyl) imidazole ion liquid and chlorination 1; 3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid is a monomer with these two kinds of ionic liquids, at catalyst S nCl then
2Through the method for melt phase polycondensation, the synthesizing new main chain contains the ion liquid polymer poly ion liquid of imidazoles down in effect.
It specifically synthesizes and comprises following process step:
1. chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid---[hhIm]
+Cl
-Synthetic
With imidazoles and ethylene chlorhydrin mixed in molar ratio, add the absolute ethyl alcohol of 2～2.5 times of molar weights of total amount, the sodium Metal 99.5 of 0.05～0.07 times of molar weight, under agitation with 1: 2～1: 2.2; In-1～2 ℃ of reactions 7～8 hours, be warming up to 10～60 ℃ then, behind reaction 40～48h; Filtration obtains lurid liquid; Boil off the intact ethylene chlorhydrin of methanol solvate and unreacted, then in 0～-2 ℃ freezing 40～48 hours, promptly get with the ETHYLE ACETATE washing.Its reaction equation is following:
With chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid is dissolved in the methyl alcohol, to wherein adding chlorination 1; 8～10 times of gacs of 3-two (2-hydroxyethyl) imidazole ion liquid quality were under agitation placed 40～48 hours, filtered; Filtrating is boiled off partial solvent, under 0～-1 ℃, leave standstill 40～48h, crystallization; Filter, obtain the chlorination 1 of purifying, 3-two (2-hydroxyethyl) imidazole ion liquid.
Monomer [hhim]
+Cl
-Ion liquid nuclear-magnetism characterizes as follows:
1H-NMR (400MHz, δ, ppm; Solvent is D
2O)
a1(δ＝7.4-7.5H1)b1(δ＝6.79-6.93H4)c1(δ＝3.87H4)d1(δ＝3.59H4)e1(δ＝4.6H1)
Wherein a1, b1, c1, d1, e1 represent the position of the H that marks respectively.
Monomer ion [hhim]
+Cl
-Ir data following:
3107.89cm
-1Be c-H vibration absorption peak on the imidazole ring, 2947.58cm
-12845cm
-1Be the c-H vibration absorption peak on the methylene radical on the imidazole ring, 1573.80cm
-1Be c=H vibration absorption peak on the imidazole ring, 3313.77cm
-1Vibration absorption peak for-OH.
2. chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid---[eeIm]
+Cl
-Synthetic
Said chlorination 1, the compound method of 3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid is: with imidazoles and the methyl chloroacetate mixed in molar ratio with 1: 2～1: 2.2, add the sodium Metal 99.5 of 2～2.5 times of molar weight absolute ethyl alcohols of total amount, 0.05～0.07 times of molar weight; Under agitation; In-1～0 ℃ of back flow reaction 5～7 hours, be warming up to 10～60 ℃ then, behind reaction 22～24h; Filtration obtains lurid liquid; Boil off the intact methyl chloroacetate of methanol solvate and unreacted, then in 0～-2 ℃ freezing 40～48 hours, promptly get with the ETHYLE ACETATE washing at last.Its reaction equation is following:
With chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazol ion liquid is dissolved in respectively in the methyl alcohol, to wherein adding chlorination 1; 3-two (2-methoxyl group-2-oxygen ethyl) 8～10 times of gacs of imidazol ion liquid quality were under agitation placed 40～48 hours, filtered; Filtrating is boiled off partial solvent, under 0～-1 ℃, leave standstill 40～48h, crystallization; Filter, obtain the chlorination 1 of purifying, 3-two (2-methoxyl group-2-oxygen ethyl) imidazol ion liquid.
Chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid [eeim]
+Cl
-Nuclear magnetic resonance data following:
1H-NMR(400MHz，δ，ppm；D
2O)，a2(δ＝8.7-8.9H1)b2(δ＝7.2-7.4H2)c2(δ＝5.0-5.2H3)d2(δ＝3.5-3.8H6)。
Wherein a2, b2, c2, d2 represent the position of the H that marks respectively.
Monomer ion [eeim]
+Cl
-Ir data following:
3107.89cm
-1Be c-H vibration absorption peak on the imidazole ring, 2956.58cm
-12845cm
-1Be the c-H vibration absorption peak on the methylene radical on the imidazole ring, 1573.80cm
-1Be c=H vibration absorption peak on the imidazole ring, 1750.69cm
-1Be the vibration absorption peak of C=O, 3107.89cm
-1For the carbonyl first line of a couplet-CH
3Vibration absorption peak.
3. ion liquid polymer synthetic that contains imidazoles on the main chain
At N
2Protection down, with chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid and chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid is with 1: 1～1: 1.1 mixed in molar ratio, the SnCl of 0.02～0.03 times of molar weight of adding total amount
2, being warming up to 140～150 ℃, reaction 2.5～3h continues to be warming up to 160～180 ℃, extracts the methyl alcohol that reaction generates out; Cooling obtains the glassy yellow material, uses earlier water dissolution, and the back obtains jonquilleous polymkeric substance with ETHYLE ACETATE washing, vacuum-drying.Reaction equation is following:
Three, the sign of ion liquid polymer:
1, the nuclear-magnetism of ion liquid polymer characterizes as follows:
Wherein, a2, b2, c2, d2, e2, f2, g2, h2, i2, m2, n2, o2, p2 are for marking the position of hydrogen.The nuclear magnetic spectrum of liquid ionomer of the present invention is seen Fig. 1.
1H-NMR (400MHz, δ, ppm; Solvent is D
2O) c2 h2 (δ=8.6 H2) i2 m2 n2o2 (δ=7.4 H2) f2 (δ=5.1 H2) p2 (δ=3.6 H3) b2 d2 (δ=4.0-4.2 H4) a2 e2 (the f2 g2 (δ=4.8 H4) of δ=3.7H4).
2, the IR Characterization of polymkeric substance is following:
At 1752.16cm
-1Be the characteristic peak of ester group, 3334.25cm
-1Be the characteristic honeybee of the terminal hydroxy group of polymkeric substance, 2955.49cm
-1Be saturated hydrocarbon characteristic peak, 1626.14cm
-1Be the characteristic peak of the stretching vibration of (C=N), 1226cm
-1Stretching vibration characteristic peak for (C-O-C).The infared spectrum of polymkeric substance of the present invention is seen Fig. 2.
3, the DTA of polymkeric substance characterizes
Polymkeric substance HEP is prevented into vacuum drying oven temperature is set at 80 ℃, dry 48 hours, at N
2Protection down, temperature rise rate is 5 ℃/min, the beginning room temperature is raised to 120 ℃, removing can absorbent moisture content, then at N
2Protection is cool to room temperature down, begins to warm to 400 ℃ again.The curve of DTA shows that polymkeric substance begins to decompose weightlessness at 230 ℃, and is complete to 280 ℃ of weightlessness.The DTA curve of polymkeric substance of the present invention is seen Fig. 3.
4, the reckoning of polymericular weight
According to the relation that peak area and the number of its corresponding H are directly proportional, calculate n=9, the molecular weight of polymkeric substance is about 3700.N=20, the molecular weight of polymkeric substance is about 8100.
This novel ion liquid polymerization thing is a monomer with the functional ion liquid that has hydroxyl and ester group, obtains main chain through condensation polymerization and contains the unitary polyester of ionic liquid, through condition that changes polyreaction and the polymkeric substance that catalyzer can prepare molecular weight 4700～8100.
Four, the property testing of ion liquid polymer
The mensuration of electric conductivity:
Adopt TH2818 Automatic Component Analyzer to measure, temperature is 20 ℃
Measure the result: electric conductivity: 5.4～7.2 * 10
-5S/m.
The above results shows that synthetic ion liquid polymer of the present invention has reasonable conductivity.Because the unitary introducing of ionic liquid, this new polymers is at polyelectrolyte, and aspects such as gas separation membrane all have application prospect.
Description of drawings
Fig. 1 is the nuclear magnetic spectrum of polymkeric substance of the present invention
Fig. 2 is the infared spectrum of polymkeric substance of the present invention
Fig. 3 is the DTA curve of polymkeric substance of the present invention
Embodiment
Further specify the synthesis technique that contains the ion liquid polymer of imidazoles on the main chain of the present invention through concrete experiment below.
1. chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid---[hhIm]
+Cl
-Synthetic
Magnetic agitation is being housed, reflux condensing tube, N
2The three-necked flask of the 250ml of conduit, the absolute ethyl alcohol of adding 100ml, the sodium Metal 99.5 of 4.7g is put into ice-water bath with three-necked flask; Reacted about 6 hours, and after question response is intact, added the imidazoles of 0.2mol; Ethylene chlorhydrin (time spent is underpressure distillation again) with 0.42mol slowly drips with tap funnel again, and reaction 7h takes out three-necked flask from ice-water bath; React 24h down at 20 ℃, filter, obtain lurid liquid; Boil off methanol solvate and the intact ethylene chlorhydrin of unreacted with Rotary Evaporators, with the ETHYLE ACETATE washing for several times, obtain lurid liquid.
To obtain lurid liquid [hhIm]
+Cl
-Be dissolved in the methyl alcohol, to wherein adding [hhIm]
+Cl
-The gac that quality is 2 times is under agitation placed 48h, filters, and filtrating is boiled off partial solvent, in refrigerator, places 48h then, and crystallization is filtered and obtained white solid, [hhIm]
+The Cl productive rate is 79.2%.
2. chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid---[eeIm]
+Cl
-Synthetic
Magnetic agitation is being housed, reflux condensing tube, N
2The three-necked flask of the 250ml of conduit, the anhydrous methanol of adding 100ml, the sodium Metal 99.5 of 4.7g is put into ice-water bath with three-necked flask; Reacted about 7 hours, after question response is intact, the imidazoles of 0.2mol; The methyl chloroacetate (time spent is underpressure distillation again) of 0.42mol is slowly dripped with tap funnel, and reaction 7h takes out three-necked flask from ice-water bath; React 48h down at 20 ℃, filter, obtain lurid liquid; Boil off methanol solvate and methyl chloroacetate with Rotary Evaporators, with the ETHYLE ACETATE washing for several times, obtain lurid liquid.
To obtain lurid liquid [eeIm]
+Cl
-Be dissolved in the methyl alcohol, to the gac of 2 times of liquid masies wherein, under agitation place 48h, filter, filtrating is boiled off partial solvent, in refrigerator, place 48h then, crystallization is filtered and is obtained white solid, [eeIm]
+Cl
-Productive rate is 76.2%.
3. ion liquid polymer synthetic that contains imidazoles on the main chain
Get 0.2mol [eeIm] respectively
+Cl
-[hhIm]
+Cl
-, the SnCl of 0.03g
2In three flasks of 50ml, load onto water distilling apparatus, with water pump it being evacuated earlier rushes to N
2Protection lets temperature slowly be raised to 140 ℃ of reaction 3h, takes out 3h with oil pump at 180 ℃, extracts the methyl alcohol that reaction generates out, at N
2Down cooling of protection, obtain the glassy yellow material, with less water it is dissolved, the ETHYLE ACETATE washing for several times, dry 24h in vacuum drying oven obtains jonquilleous polymkeric substance, promptly gets the ion liquid polymer that contains imidazoles on the main chain of the present invention.Productive rate is 80.1%.
Claims (2)
1. a main chain contains the ion liquid polymer of imidazoles, and its chemical structural formula is following:
N=9～20 wherein, the molecular weight of polymkeric substance is 3700～8100.
2. main chain contains the compound method of the ion liquid polymer of imidazoles according to claim 1; Be earlier with imidazoles respectively with ethylene chlorhydrin, it is synthesizing chlorinated 1 that methyl chloroacetate reacts, 3-two (2-hydroxyethyl) imidazole ion liquid; Chlorination 1; 3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid is a monomer with these two kinds of ionic liquids, at catalyst S nCl then
2Effect under carry out melt phase polycondensation and form; Specific as follows:
1. chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid---[hhIm]
+Cl
-Synthetic
Magnetic agitation is being housed, reflux condensing tube, N
2The three-necked flask of the 250ml of conduit, the absolute ethyl alcohol of adding 100ml, the sodium Metal 99.5 of 4.7g is put into ice-water bath with three-necked flask; Reacted 6 hours, and after question response is intact, added the imidazoles of 0.2mol; Ethylene chlorhydrin with 0.42mol slowly drips with tap funnel again, and reaction 7h takes out three-necked flask from ice-water bath; React 24h down at 20 ℃, filter, obtain lurid liquid; Boil off methanol solvate and the intact ethylene chlorhydrin of unreacted with Rotary Evaporators, with the ETHYLE ACETATE washing for several times, obtain lurid liquid;
To obtain lurid liquid [hhIm]
+Cl
-Be dissolved in the methyl alcohol, to wherein adding [hhIm]
+Cl
-The gac that quality is 2 times is under agitation placed 48h, filters, and filtrating is boiled off partial solvent, in refrigerator, places 48h then, and crystallization is filtered and obtained white solid; [hhIm]
+The Cl productive rate is 79.2%;
2. chlorination 1, and 3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid---[eeIm]+Cl-'s is synthetic
Magnetic agitation is being housed, reflux condensing tube, N
2The three-necked flask of the 250ml of conduit, the anhydrous methanol of adding 100ml, the sodium Metal 99.5 of 4.7g is put into ice-water bath with three-necked flask; Reacted 7 hours, after question response was intact, the imidazoles of 0.2mol slowly dripped the methyl chloroacetate of 0.42mol with tap funnel; Reaction 7h takes out three-necked flask from ice-water bath, react 48h down at 20 ℃, filters; Obtain lurid liquid, boil off methanol solvate and methyl chloroacetate, with the ETHYLE ACETATE washing for several times, obtain lurid liquid with Rotary Evaporators;
With the lurid liquid [eeIm] that obtains
+Cl
-Be dissolved in the methyl alcohol, to the gac of 2 times of liquid masies wherein, under agitation place 48h, filter, filtrating is boiled off partial solvent, in refrigerator, place 48h then, crystallization is filtered and is obtained white solid; [eeIm]
+Cl
-Productive rate is 76.2%;
3. ion liquid polymer synthetic that contains imidazoles on the main chain
Get 0.2mol [eeIm] respectively
+Cl
-[hhIm]
+Cl
-, the SnCl of 0.03g
2In three flasks of 50ml, load onto water distilling apparatus, with water pump it being evacuated earlier rushes to N
2Protection lets temperature slowly be raised to 140 ℃ of reaction 3h, takes out 3h with oil pump at 180 ℃, extracts the methyl alcohol that reaction generates out, at N
2Down cooling of protection, obtain the glassy yellow material, with less water it is dissolved, the ETHYLE ACETATE washing for several times, dry 24h in vacuum drying oven obtains jonquilleous polymkeric substance, promptly gets the ion liquid polymer that contains imidazoles on the main chain, productive rate is 80.1%.
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| CN102127196B (en) * | 2011-01-10 | 2012-06-13 | 浙江大学 | Ionic liquid segmented copolymer with imidazole-contained main chain and preparation method thereof |
| CN103665369B (en) * | 2012-09-14 | 2016-04-13 | 中国科学院兰州化学物理研究所 | A kind of polyoxyethylene glycol functionalization polyoxometalate ionic liquid and preparation method thereof |
| US20230131111A1 (en) * | 2020-05-26 | 2023-04-27 | Nanyang Technological University | Biodegradable polyimidazoliums and oligoimidazoliums |
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