CN101255226A - 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
- Publication number
- CN101255226A CN101255226A CNA2008100178225A CN200810017822A CN101255226A CN 101255226 A CN101255226 A CN 101255226A CN A2008100178225 A CNA2008100178225 A CN A2008100178225A CN 200810017822 A CN200810017822 A CN 200810017822A CN 101255226 A CN101255226 A CN 101255226A
- Authority
- CN
- China
- Prior art keywords
- ion liquid
- chlorination
- imidazole
- imidazoles
- main chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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 SnCl<SUB>2</SUB>. The ionic liquid polymer has good conductivity property (conductivity: 5.4-7.2*10<SUP>-5</SUP>S/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 the ion liquid polymer and the synthetic method thereof of the novel symmetric function of class group, relate in particular to ion liquid polymer and synthetic 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 vapour pressure, 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 that hangs the ionic liquid structure on the side chain, is the macrogol ester of methacrylic acid as monomer, is to be connected with imidazole ion liquid at the polyoxyethylene glycol the other end; Monomer is the alkyl ester of methacrylic 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, have not yet to see report.
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 synthetic 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 as follows:
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, be monomer with these two kinds of ionic liquids then, at catalyst S nCl
2By 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 processing step:
1. chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid---[hhIm]
+Cl
-Synthetic
With imidazoles and ethylene chlorhydrin mixed in molar ratio with 1: 2～1: 2.2, add the dehydrated 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, 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, with the ethyl acetate washing promptly.Its reaction equation is as follows:
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, under agitation placed 40～48 hours, filter, filtrate 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 as follows:
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
Described chlorination 1, the synthetic 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, the sodium Metal 99.5 that adds 2～2.5 times of molar weight dehydrated 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 at last with ethyl acetate washing.Its reaction equation is as follows:
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, under agitation placed 40～48 hours, filter, filtrate 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 as follows:
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 as follows:
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 ethyl acetate washing, vacuum-drying.Reaction equation is as follows:
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) c2h2 (i2m2n2o2 of δ=the 8.6H2) (f2 of δ=the 7.4H2) (p2 of δ=the 5.1H2) (b2d2 of δ=the 3.6H3) (a2e2 of δ=the 4.0-4.2H4) (f2g2 of δ=3.7H4) (δ=4.8H4).
2, the Infrared Characterization of polymkeric substance is as follows:
At 1752.16cm
-1Be the characteristic peak of ester group, 3334.25cm
-1Be the feature 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, by 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 ℃
Measurement 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 below by concrete experiment.
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 dehydrated alcohol that adds 100ml, 4.7g sodium Metal 99.5, three-necked flask is put into ice-water bath, reacted about 6 hours, after question response is intact, add the imidazoles of 0.2mol, the ethylene chlorhydrin (time spent is underpressure distillation again) with 0.42mol slowly drips with dropping funnel again, reaction 7h, from ice-water bath, take out three-necked flask, react 24h down, filter at 20 ℃, obtain lurid liquid, boil off methanol solvate and the intact ethylene chlorhydrin of unreacted with Rotary Evaporators, with the ethyl 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 filtrate is boiled off partial solvent, places 48h then in refrigerator, 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 that adds 100ml, 4.7g sodium Metal 99.5, three-necked flask is put into ice-water bath, reacted about 7 hours, after question response was intact, the imidazoles of 0.2mol slowly dripped the methyl chloroacetate (time spent is underpressure distillation again) of 0.42mol with dropping funnel, reaction 7h, from ice-water bath, take out three-necked flask, react 48h down, filter at 20 ℃, obtain lurid liquid, boil off methanol solvate and methyl chloroacetate with Rotary Evaporators, with the ethyl 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, filtrate is boiled off partial solvent, place 48h then in refrigerator, 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 allows 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 ethyl 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 (6)
1, a kind of main chain contains the ion liquid polymer of imidazoles, and its chemical structural formula is as follows:
N=9～20 wherein, the molecular weight of polymkeric substance is 3700～8100.
2, main chain contains the synthetic method of the ion liquid polymer of imidazoles according to claim 1, be earlier with imidazoles respectively with ethylene chlorhydrin, methyl chloroacetate reacts synthesizing chlorinated 1,3-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.
3, the preparation method who contains the ion liquid polymer of imidazoles as main chain as described in the claim 2, it is characterized in that: described chlorination 1, the synthetic method of 3-two (2-hydroxyethyl) imidazole ion liquid is: with imidazoles and the ethylene chlorhydrin mixed in molar ratio with 1: 2～1: 2.2, the dehydrated alcohol that adds 2～2.5 times of molar weights of total amount, 0.05 the sodium Metal 99.5 of～0.07 times of molar weight, under agitation, 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, with the ethyl acetate washing promptly.
4, the preparation method who contains the ion liquid polymer of imidazoles as main chain as described in the claim 2, it is characterized in that: described chlorination 1, the synthetic 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 2～2.5 times of molar weight anhydrous methanols of total amount, 0.05 the sodium Metal 99.5 of～0.07 times of molar weight, under agitation, in-1～0 ℃ of 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 at last with ethyl acetate washing.
5, the preparation method who contains the ion liquid polymer of imidazoles as main chain as described in the claim 2, it is characterized in that: described chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid and chlorination 1, the method that the synthetic main chain of 3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid melt phase polycondensation contains the ion liquid polymer of imidazoles is: 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 ethyl acetate washing, vacuum-drying.
6, the preparation method who contains the ion liquid polymer of imidazoles as main chain as described in the claim 5, it is characterized in that: before melt phase polycondensation with chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid, chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazole ion liquid adopts following technology to carry out purifying: with chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid, chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazol ion liquid is dissolved in the methyl alcohol respectively, to wherein adding chlorination 1,3-two (2-hydroxyethyl) imidazole ion liquid, chlorination 1, the gac of 3-two (2-methoxyl group-2-oxygen ethyl) imidazol ion liquid quality 8～10, under agitation placed 40～48 hours, filter, filtrate is boiled off partial solvent, under 0～-1 ℃, leave standstill 40～48h, crystallization, filter, obtain the chlorination 1 of purifying respectively, 3-two (2-hydroxyethyl) imidazole ion liquid, chlorination 1,3-two (2-methoxyl group-2-oxygen ethyl) imidazol ion liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100178225A CN101255226B (en) | 2008-03-21 | 2008-03-21 | Ionic liquid polymer containing imidazole in main chain and method for synthesizing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100178225A CN101255226B (en) | 2008-03-21 | 2008-03-21 | Ionic liquid polymer containing imidazole in main chain and method for synthesizing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101255226A true CN101255226A (en) | 2008-09-03 |
| CN101255226B CN101255226B (en) | 2012-06-20 |
Family
ID=39890365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100178225A Expired - Fee Related CN101255226B (en) | 2008-03-21 | 2008-03-21 | Ionic liquid polymer containing imidazole in main chain and method for synthesizing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101255226B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367912B (en) * | 2008-09-29 | 2011-05-04 | 西北师范大学 | Modified polyester fibre with excellent hydrophilic and electrostatic capability, and method of preparing the same |
| CN102127196A (en) * | 2011-01-10 | 2011-07-20 | 浙江大学 | Ionic liquid segmented copolymer with imidazole-contained main chain and preparation method thereof |
| CN103665369A (en) * | 2012-09-14 | 2014-03-26 | 中国科学院兰州化学物理研究所 | Polyethylene glycol functionalized polyoxometalate ionic liquid and preparation method thereof |
| WO2021242174A1 (en) * | 2020-05-26 | 2021-12-02 | Nanyang Technological University | Biodegradable polyimidazoliums and oligoimidazoliums |
-
2008
- 2008-03-21 CN CN2008100178225A patent/CN101255226B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367912B (en) * | 2008-09-29 | 2011-05-04 | 西北师范大学 | Modified polyester fibre with excellent hydrophilic and electrostatic capability, and method of preparing the same |
| CN102127196A (en) * | 2011-01-10 | 2011-07-20 | 浙江大学 | Ionic liquid segmented copolymer with imidazole-contained main chain and preparation method thereof |
| 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 |
| CN103665369A (en) * | 2012-09-14 | 2014-03-26 | 中国科学院兰州化学物理研究所 | Polyethylene glycol functionalized polyoxometalate ionic liquid 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 |
| WO2021242174A1 (en) * | 2020-05-26 | 2021-12-02 | Nanyang Technological University | Biodegradable polyimidazoliums and oligoimidazoliums |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101255226B (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109320692B (en) | polyfluorene alkylene containing cation group and no ether bond, preparation method thereof and anion exchange membrane | |
| CN101255226B (en) | Ionic liquid polymer containing imidazole in main chain and method for synthesizing same | |
| WO2015032113A1 (en) | Metalporphyrin complex, preparation method therefor and method for preparing polycarbonate | |
| CN103274908B (en) | Bisphenol monomer containing bi-tert-butyl and fluorenyl structure, and preparation method and application thereof | |
| CN108358767B (en) | Pentabenzyl benzene-containing difluoride monomer, preparation method and application thereof in polyaryletherketone functional film | |
| CN106876758B (en) | A kind of preparation method of the proton exchange membrane with hydrophilic/hydrophobic inierpeneirating network structure | |
| CN104744306A (en) | P-chloroaniline isocyanate preparation method | |
| CN108530660B (en) | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof | |
| JP2017511415A (en) | Hydroxide stable ionene | |
| CN108727402A (en) | A kind of oxa- loop coil bridging urea groups pyrimidinone compound and its synthetic method | |
| CN101220137B (en) | Hyperbranched polyaromatic hydrocarbon containing pyridine rings and method for producing the same | |
| CN107573501A (en) | A kind of cross-linking fluorine-containing sulfonated polyether compound and preparation method thereof | |
| CN109053474B (en) | Flexible diamine monomer, preparation method thereof and application thereof in preparation of polyimide | |
| CN104277216A (en) | Sulfonated perfluorocyclobutyl polyarylether polymers as well as preparation method and application thereof | |
| CN102127196B (en) | Ionic liquid segmented copolymer with imidazole-contained main chain and preparation method thereof | |
| CN112608472A (en) | Terminal functionalized polymer and method for carrying out CuAAC polymerization by utilizing copper acetylide | |
| CN108948349A (en) | A kind of spiro polymer material and preparation method thereof | |
| CN103102369B (en) | A kind of production method of diethyl ethylphosphate | |
| CN104262616A (en) | Perfluoro-cyclobutyl polyarylether polymer containing 1H-1,2,3-triazole group, as well as preparation method and application thereof | |
| CN112625160B (en) | End group functionalized polymer and method for carrying out Glaser coupling polymerization reaction by utilizing copper acetylide | |
| CN109456422B (en) | Hyperbranched hemicellulose polymer and preparation method and application thereof | |
| CN106631751B (en) | More two fluorine monomers of methyl chains of anti-oxidative and preparation method thereof | |
| CN101250159B (en) | Chloride 1,3-di(2-methoxy-2-yloxyethyl) imidazole ionic liquid and method for synthesizing same | |
| CN107151324A (en) | Poly- fragrant imines ether sulfone of thermal response fluorescent type and preparation method thereof | |
| CN108409927A (en) | A kind of irriidazole-functionalized polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120620 Termination date: 20130321 |