CN101255226B - Ionic liquid polymer containing imidazole in main chain and method for synthesizing same - Google Patents

Abstract

The invention provides a kind of synthetic method of the ionic liquid polymer containing imidazole in the main chain, it first reacts with imidazole respectively with 2-chloroethanol, methyl chloroacetate to synthesize chlorinated 1,3-bis(2-hydroxyethyl) Imidazolium ionic liquid, chloride 1,3-bis(2-methoxy-2-oxyethyl) imidazolium ionic liquid, then use these two ionic liquids as monomers, carry out melt polycondensation under the effect of catalyst _SnCl become. Experiments prove that the ionic liquid polymer synthesized by the present invention has good electrical conductivity (conductivity: 5.4˜7.2×10 ⁻⁵ S/m.). Due to the introduction of the ionic liquid unit, the new polymer has application prospects in polyelectrolyte, gas separation membrane and so on.

Description

Main chain contains the ion liquid polymer and the compound method thereof of imidazoles

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 kind of main chain contains the ionic liquid polymer of imidazole, and its chemical structural formula is as follows:

Where n=9-20, the molecular weight of the polymer is 3700-8100. 2. as claimed in claim 1, the main chain contains the synthetic method of the ionic liquid polymer of imidazole, is to react with imidazole respectively with 2-chloroethanol, methyl chloroacetate to synthesize chlorinated 1,3-bis (2-hydroxyethyl ether) base) imidazole ionic liquid, chlorinated 1,3-two (2-methoxyl-2-oxyethyl) imidazole ionic liquid, then use these two ionic liquids as monomers, melt under the effect of catalyst _SnCl Formed by polycondensation; the details are as follows: ①Synthesis of 1,3-bis(2-hydroxyethyl)imidazolium chloride ionic liquid—[hhIm] ⁺ Cl ^- In the 250ml three-necked flask equipped with magnetic stirring, reflux condenser, and _N2 conduit, add 100ml of absolute ethanol, 4.7g of metallic sodium, put the three-necked flask into an ice-water bath, react for 6 hours, and wait for the reaction to complete Finally, add 0.2 mol of imidazole, then slowly add 0.42 mol of 2-chloroethanol dropwise with a dropping funnel, react for 7 hours, take out the three-necked flask from the ice-water bath, react at 20°C for 24 hours, and filter to obtain light yellow The liquid was evaporated with a rotary evaporator to remove the methanol solvent and unreacted 2-chloroethanol, and washed several times with ethyl acetate to obtain a light yellow liquid; Will obtain pale yellow liquid [hhIm] ⁺ Cl ^- dissolve in methanol, add [hhIm] ⁺ Cl ^- the active carbon of 2 times of quality wherein, place 48h under stirring, filter, the filtrate is evaporated part solvent, then in refrigerator placed in 48h, crystallized, and filtered to obtain a white solid; [hhIm] ⁺ Cl yield was 79.2%; ②1,3-bis(2-methoxy-2-oxyethyl)imidazolium chloride ionic liquid——synthesis of [eeIm]+Cl- In the 250ml three-necked flask equipped with magnetic stirring, reflux condenser, and _N2 conduit, add 100ml of anhydrous methanol and 4.7g of metallic sodium, put the three-necked flask into an ice-water bath, and react for 7 hours until the reaction is complete Finally, 0.2 mol of imidazole, 0.42 mol of methyl chloroacetate was slowly added dropwise with a dropping funnel, reacted for 7 hours, took out the three-necked flask from the ice-water bath, reacted at 20°C for 48 hours, and filtered to obtain a light yellow liquid , evaporate methanol solvent and methyl chloroacetate with a rotary evaporator, and wash with ethyl acetate several times to obtain a light yellow liquid; Dissolve the obtained light yellow liquid [eeIm] ^{+ Cl} in methanol, add activated carbon with 2 times the liquid mass, place it under stirring for 48 hours, filter, evaporate part of the solvent from the filtrate, then place it in the refrigerator for 48 hours, and crystallize , filtered to obtain a white solid; [eeIm] ⁺ Cl ^- yield was 76.2%; ③Synthesis of ionic liquid polymers containing imidazole in the main chain Take 0.2mol of [eeIm] ⁺ Cl ^- and [hhIm] ⁺ Cl ^- respectively, and put 0.03g of SnCl ₂ in a 50ml three-flask, install a distillation device, first pump it into a vacuum with a water pump and flush it with N ₂ for protection. Allow the temperature to rise slowly to 140°C for 3 hours, pump at 180°C for 3 hours with an oil pump, extract the methanol produced by the reaction, and cool under the protection of _N2 to obtain a bright yellow substance, which is dissolved in a small amount of water and washed with ethyl acetate for several Next, dry in a vacuum oven for 24 hours to obtain a bright yellow polymer, that is, an ionic liquid polymer containing imidazole in the main chain, with a yield of 80.1%.

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