CN105131271B - Poly ion liquid type basic indicator and its preparation suitable for non-polar solven - Google Patents
Poly ion liquid type basic indicator and its preparation suitable for non-polar solven Download PDFInfo
- Publication number
- CN105131271B CN105131271B CN201510493337.5A CN201510493337A CN105131271B CN 105131271 B CN105131271 B CN 105131271B CN 201510493337 A CN201510493337 A CN 201510493337A CN 105131271 B CN105131271 B CN 105131271B
- Authority
- CN
- China
- Prior art keywords
- ion liquid
- polar solven
- liquid type
- poly ion
- type basic
- 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.)
- Expired - Fee Related
Links
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention provides a kind of poly ion liquid type basic indicator suitable for non-polar solven and preparation method thereof, it is characterised in that comprise the following steps：Eliminating water deoxygenation process is carried out to reaction vessel；Phthalic anhydride and N, N dimethylformamide are added in reaction vessel under nitrogen protection；Ethylene glycol, stirring are added under nitrogen protection；Epoxychloropropane is added in the solution for obtaining, is reacted under agitation；N methylimidazole is added, is reacted under agitation；The mixture for obtaining is added in acetone, stirring, precipitation；By precipitation dissolving in deionized water, it is added drop-wise in the methyl blue aqueous solution, is reacted under agitation, precipitation；The precipitate with deionized water for obtaining is rinsed repeatedly, vacuum drying, be added in dichloromethane, stirring forms mixture.Filter, filtrate is obtained, vacuum drying, obtain the poly ion liquid type basic indicator suitable for non-polar solven.The polymer can be used for the alkaline instruction field in non-polar solven.
Description
Technical field
The present invention relates to a kind of basic indicator of chemical technology field, specifically, refers to one kind nonpolar
The preparation method of the poly ion liquid type indicator of function is indicated in solvent with alkalescence.
Background technology
Ionic liquid is a kind of ionic compound being in a liquid state in room temperature or under being close to room temperature.From ionic liquid before 100 years
Reported for the first time, the application of ionic liquid has covered numerous areas, such as fine chemistry industry, separating-purifying, electrochemistry, solar energy
Battery, bio-medical etc..In recent years, the poly ion liquid for being developed by ionic liquid is in polymer chemistry and material science
Field has attracted huge concern.Poly ion liquid is the polymer with anions and canons electrolyte group on repetitive.Poly-
Ionic liquid have ionic liquid low melting point, low-vapor pressure, good conductivity, good stability, recyclable, nontoxic pollution-free excellent
Characteristic and main polymer chain mechanical stability are good, processability is good, chemical compatibility is good, good endurance, space navigability are strong
Excellent properties.More than that, poly ion liquid has more very excellent ion interchangeability, is handed over by simple ion
Change, large quantities of new functional poly ionic liquids can be prepared.The application of poly ion liquid is increasingly extensive, such as conduct point
Powder, consisting of phase-transferring agent, adsorbent, release agent, ion conductive material, nano composite material, bio-medical material etc..
Poly ion liquid type basic indicator suitable for non-polar solven is referred at non-polar solven (as dichloromethane)
In with alkali mutagens color with reach indicate function new poly ion liquid.Original water soluble anion indicator (as methyl blue)
Water and these polar solvents of methyl alcohol can only be dissolved in, even if the current research to poly ion liquid type basic indicator is also mainly concentrated
In the aqueous solution, methyl alcohol, these polar solvent environment of acetone, and in non-polar solven with alkalescence indicate function gather from
There is not been reported for sub- liquid.Therefore how using commercialization raw material, prepared suitable for non-polar solven using simple method
Poly ion liquid type basic indicator, will be very meaningful.
Find through the literature search to prior art, poly ion liquid type basic indicator will be mainly by indicating function
Group is connected to the repetitive of main polymer chain and is able to preparation and completes.Jiangna Guo et al. exists《Polymer
Chemistry》2013 page 1309 to page 1312 of volume 4 delivered " Plastic reusable pH indicator
strips:preparation via anion-exchange of poly(ionic liquids)with anionic
Dyes " (by carrying out, with anionic dye, the plasticity pH test paper that can be used repeatedly that anion exchange is prepared), this article
Author has synthesized cross-linked polymer first, has synthesized dye molecule in utilization and anionic dye anion exchange and has been difficult leakage
Polymer pH test paper, its all have good alkaline indicating effect in the aqueous solution with some polar organic solvents.Due to gather from
Therefore the research of the liquid basified indicator of son be specially adapted for the polyion liquid of non-polar solven still in the stage of continuous development
Build basic indicator does not appear in the newspapers so far.
Content of the invention
It is an object of the invention to the suitable solvents scope of developing poly ion liquid type basic indicator, sets with molecule
Meter, has obtained a kind of poly ion liquid type basic indicator solvable and indicating function with alkalescence in non-polar solven.
The present invention is achieved by the following technical solutions, the present invention with ethylene glycol as initiator, phthalic anhydride and
Epoxychloropropane monomer is raw material, using alternately ring-opening polymerisation, synthesizes the linear polyesters as shown in formula (1), then by N- methyl
Imidazoles is grafted to polyester repetitive, prepares the linear poly ion liquid (PIL-Cl) as shown in formula (2), finally utilizes
There is ion exchange with methyl blue group in PIL-Cl, so as to prepare the anion as shown in formula (3) for the linear of methyl blue
Poly ion liquid PIL-MB.
The concrete technical scheme of the present invention is：
A kind of poly ion liquid type basic indicator suitable for non-polar solven, it is characterised in that its structural formula is as follows：
Wherein, n is 10-50.
The preparation method of the above-mentioned poly ion liquid type basic indicator suitable for non-polar solven, it is characterised in that
Comprise the following steps：
Step a：Eliminating water deoxygenation process is carried out to reaction vessel；
Step b：Phthalic anhydride and DMF, stirring are added in reaction vessel under nitrogen protection
Obtain the DMF solution of phthalic anhydride；
Step c：Add in the DMF solution of the phthalic anhydride in step b under nitrogen protection
Ethylene glycol, stirring；
Step d：Epoxychloropropane is added in the solution that step c is obtained, is reacted under agitation；
Step e：Remaining epoxychloropropane in the mixture for obtaining is reacted in removing step d, adds N- methylimidazole,
Reacted under stirring；
Step f：The mixture that obtains will be reacted add in acetone in step e, stirring, separation of solid and liquid are precipitated；
Step g：The precipitation obtained in step f is dissolved in deionized water, is added drop-wise in the methyl blue aqueous solution, in stirring
Under reacted, separation of solid and liquid is precipitated；
Step h：The precipitate with deionized water obtained in step g is rinsed repeatedly, vacuum drying, be added to dichloromethane
In, stirring forms mixture.
Step i：The mixture obtained in step h is filtered, filtrate is obtained, rotary evaporation removes dichloromethane solvent, very
Empty dry, obtain the poly ion liquid type basic indicator suitable for non-polar solven.
Preferably, the concentration of the DMF solution of the phthalic anhydride in described step b is 0.1-1
Grams per milliliter.
Preferably, in described step c, it is 1%-2% that described ethylene glycol accounts for the mole percent of phthalic anhydride.
Preferably, in described step d, described epoxychloropropane is 1-1.3 with the mol ratio of phthalic anhydride:1.
Preferably, in described step d, reacted under described stirring, its temperature is 95-120 DEG C, its reaction time
For 10-12 hour.
Preferably, N, the N- diformazan of the phthalic anhydride in the N- methylimidazole for adding in described step e and step b
The mol ratio of the phthalic anhydride in base formamide solution is 1.1-1.5:1.
Preferably, in described step e, reacted under the stirring, its reaction temperature is 80-95 DEG C, during its reaction
Between be 4-6 days.
Preferably, in described step f, the volume ratio of the mixture obtained in the acetone and step e is 9-13:1.
Preferably, in described step g, the methyl orange precipitates the TMSIM N imidazole base in (PIL-Cl) with gained in step f
The mol ratio of group is 1.2-1.8:1.
Preferably, in described step g, reacted under the stirring, its reaction temperature is 5-25 DEG C, its reaction time
For 10-20 hour.
Preferably, in described step h, the whipping temp is 5-40 DEG C, and its time is 5-10 hour.
Preferably, the ratio of precipitation and dichloromethane after being vacuum dried in described step h is 1g:0.05-1L.
The principle of the present invention is the ring-opening reaction that acid anhydrides first occurs with phthalic anhydride using initiator ethylene glycol, acid anhydrides
Open-loop products carry out the ring-opening reaction of epoxy with epoxychloropropane, and epoxy addition product carries out acid anhydrides with phthalic anhydride again
Ring-opening reaction, repeated open loop are reacted, and obtain polyester product, then N- methylimidazole are connected to polyester repetition by graft reaction
Unit, is obtained poly ion liquid PIL-Cl of the anion for chlorion, is carried out with chlorion group finally by methyl orange group
Ion exchange, methyl orange group is connected on N- methylimidazole group, prepares the polyion suitable for non-polar solven
Liquid-type basic indicator.Gained is applied to the molecular structure of the poly ion liquid type basic indicator of non-polar solven and can lead to
Cross nuclear magnetic resoance spectrum to determine.Poly ion liquid type basic indicator in non-polar solven alkalescence indicate function by ultraviolet can
See that spectrophotometer is measured.And infrared spectrum, gel permeation chromatography, differential scanning calorimetry, thermal weight loss etc. can be used as auxiliary
Analysis means.
Poly ion liquid type basic indicator suitable for non-polar solven prepared in accordance with the present invention, its cost of material are low
Honest and clean, convieniently synthesized, reaction controllability is good.The polymer has good heat endurance, can show bright in non-polar solven
Aobvious alkalescence indicates function.In view of which is with preferable dissolubility and obvious alkalescence indication action in non-polar solven, should
Polymer can be used for the alkaline instruction field in non-polar solven.
Description of the drawings
The nuclear magnetic spectrogram of the poly ion liquid type basic indicator suitable for non-polar solven that Fig. 1 is prepared for the present invention；
Wherein：Figure a, b, c correspond to the poly ion liquid suitable for non-polar solven prepared by embodiment 1, example 2, example 3 respectively
The one-dimensional nucleus magnetic hydrogen spectrum collection of illustrative plates of type basic indicator.
The differential scanning amount of the poly ion liquid type basic indicator suitable for non-polar solven that Fig. 2 is prepared for the present invention
Thermal map.
The dissolubility test of the poly ion liquid type basic indicator suitable for non-polar solven that Fig. 3 is prepared for the present invention
Photo.
The poly ion liquid type basic indicator suitable for non-polar solven that Fig. 4 is prepared for the present invention is in different isopropylamines
Alkalescence under concentration indicates photo.
The poly ion liquid type basic indicator suitable for non-polar solven that Fig. 5 is prepared for the present invention is in different isopropylamines
Ultraviolet-visible spectrogram under concentration.
The hot weightless picture of the poly ion liquid type basic indicator suitable for non-polar solven that Fig. 6 is prepared for the present invention.
Fig. 7 is oozed through gel for the poly ion liquid type basic indicator suitable for non-polar solven prepared by embodiment 1-3
Coefficients data measured by chromatography is obtained thoroughly molecule measuring test result and corresponding n value.
Specific embodiment
Below embodiments of the invention are elaborated：This example carries out reality under premised on technical solution of the present invention
Apply, detailed embodiment and specific operating process is given, but protection scope of the present invention is not limited to following embodiments.
Embodiment 1
A kind of poly ion liquid type basic indicator suitable for non-polar solven, shown in its structural formula such as formula (3), its
In, n is 18.
The preparation method of the above-mentioned poly ion liquid type basic indicator suitable for non-polar solven is：
Step a：150 milliliters of there-necked flasks are carried out with eliminating water deoxygenation process, described eliminating water deoxygenation is processed as：By cleaning
150 milliliters of there-necked flasks are fully dried 3 hours under 90 degrees Celsius, are taken out and are cooled to room temperature, are passed through nitrogen；
Step b：Under nitrogen protection, 29.60 grams of phthalic anhydrides and 50 milliliters of N, N- are added in there-necked flask
Dimethylformamide, stirring form homogeneous solution；
Step c：0.13 gram of ethylene glycol is added (to account for phthalic anhydride in the solution for obtaining to step b under nitrogen protection
Mole percent be mole percent 1%), stirring；
Step d：18.50 grams of epoxychloropropane are added in the solution obtained to step c, are carried out anti-at 105 DEG C under stirring
Answer 10 hours；
Step e：Remaining epoxychloropropane in the mixture obtained using vacuumizing method removing step d, adds 24.63 grams
N- methylimidazole, is carried out reacting 4 day under stirring at 90 DEG C；
Step f：By in the mixture obtained in step e addition acetone, (mixture is 1 with the volume ratio of acetone:10), stir
Mix, separation of solid and liquid is carried out using the method for filtering and is precipitated；
Step g：The precipitation obtained in 0.34 gram of step f is dissolved in 50 ml deionized water, is slowly dropped to containing 1 gram
In the methyl blue aqueous solution of methyl blue and 400 ml deionized water, carry out reacting 15 hours under stirring at 10 DEG C, using filtration
Method carry out separation of solid and liquid and be precipitated；
Step h：The precipitate with deionized water obtained in step g is rinsed repeatedly, vacuum drying, 0.62 gram of precipitation is obtained,
It is added in 150 milliliters of dichloromethane, stirs 5 hours at 20 DEG C, obtain mixture.
Step i：The mixture obtained in step h is filtered, filtrate is obtained, rotary evaporation removes dichloromethane solvent, very
Empty dry, obtain the poly ion liquid type basic indicator suitable for non-polar solven.
Embodiment 2
A kind of poly ion liquid type basic indicator suitable for non-polar solven, shown in its structural formula such as formula (3), its
In, n is 21.
The preparation method of the above-mentioned poly ion liquid type basic indicator suitable for non-polar solven is：
Step a：150 milliliters of there-necked flasks are carried out with eliminating water deoxygenation process, described eliminating water deoxygenation is processed as：By cleaning
150 milliliters of there-necked flasks are fully dried 3 hours under 90 degrees Celsius, are taken out and are cooled to room temperature, are passed through nitrogen；
Step b：Under nitrogen protection, 27.00 grams of phthalic anhydrides and 50 milliliters of N, N- are added in there-necked flask
Dimethylformamide, stirring form homogeneous solution；
Step c：0.18 gram of ethylene glycol is added (to account for phthalic anhydride in the solution for obtaining to step b under nitrogen protection
Mole percent 1.5%), stirring；
Step d：16.88 grams of epoxychloropropane are added in the solution obtained to step c, are carried out anti-at 100 DEG C under stirring
Answer 10 hours；
Step e：Remaining epoxychloropropane in the mixture obtained using vacuumizing method removing step d, adds 25 grams of N-
Methylimidazole, is carried out reacting 4 day under stirring at 90 DEG C；
Step f：By in the mixture obtained in step e addition acetone, (mixture is 1 with the volume ratio of acetone:10), stir
Mix, separation of solid and liquid is carried out using the method for filtering and is precipitated；
Step g：The precipitation obtained in 0.4 gram of step f is dissolved in 50 ml deionized water, is slowly dropped to containing 1.2
In the methyl blue aqueous solution of gram methyl blue and 400 ml deionized water, carrying out reacting 15 hours under stirring at 15 DEG C, adopting
The method of filter carries out separation of solid and liquid and is precipitated；
Step h：The precipitate with deionized water obtained in step g is rinsed repeatedly, vacuum drying, 0.74 gram is obtained, add
To in 150 milliliters of dichloromethane, stir 6 hours at 20 DEG C, obtain mixture.
Step i：The mixture obtained in step h is filtered, filtrate is obtained, rotary evaporation removes dichloromethane solvent, very
Empty dry, obtain the poly ion liquid type basic indicator suitable for non-polar solven.
Embodiment 3
A kind of poly ion liquid type basic indicator suitable for non-polar solven, shown in its structural formula such as formula (3), its
In, n is 25.
The preparation method of the above-mentioned poly ion liquid type basic indicator suitable for non-polar solven is：
Step a：150 milliliters of there-necked flasks are carried out with eliminating water deoxygenation process, described eliminating water deoxygenation is processed as：By cleaning
150 milliliters of there-necked flasks are fully dried 3 hours under 90 degrees Celsius, are taken out and are cooled to room temperature, are passed through nitrogen；
Step b：Under nitrogen protection, 30.00 grams of phthalic anhydrides and 50 milliliters of N, N- are added in there-necked flask
Dimethylformamide, stirring form homogeneous solution；
Step c：0.2 gram of ethylene glycol is added (to account for phthalic anhydride in the solution for obtaining to step b under nitrogen protection
Mole percent 1.5%), stirring；
Step d：18.75 grams of epoxychloropropane are added in the solution obtained to step c, are carried out anti-at 100 DEG C under stirring
Answer 10 hours；
Step e：Remaining epoxychloropropane in the mixture obtained using vacuumizing method removing step d, adds 25 grams of N-
Methylimidazole, is carried out reacting 5 day under stirring at 90 DEG C；
Step f：By in the mixture obtained in step e addition acetone, (mixture is 1 with the volume ratio of acetone:10), stir
Mix, separation of solid and liquid is carried out using the method for filtering and is precipitated；
Step g：The precipitation obtained in 0.3 gram of step f is dissolved in 50 ml deionized water, is slowly dropped to containing 0.9
In the methyl blue aqueous solution of gram methyl blue and 400 ml deionized water, carrying out reacting 20 hours under stirring at 20 DEG C, adopting
The method of filter carries out separation of solid and liquid and is precipitated；
Step h：The precipitate with deionized water obtained in step g is rinsed repeatedly, vacuum drying, 0.58 gram of precipitation is obtained,
It is added in 150 milliliters of dichloromethane, stirs 7 hours at 20 DEG C, obtain mixture.
Step i：The mixture obtained in step h is filtered, filtrate is obtained, rotary evaporation removes dichloromethane solvent, very
Empty dry, obtain the poly ion liquid type basic indicator suitable for non-polar solven.
Embodiment result is shown in accompanying drawing：
Fig. 1 a, 1b, 1c correspond to the poly ion liquid type suitable for non-polar solven prepared by embodiment 1, example 2, example 3 respectively
The one-dimensional nucleus magnetic hydrogen spectrum collection of illustrative plates of basic indicator, the peak at wherein 3.84ppm are primary carbon proton connected with nitrogen on imidazole group
Chemical shift；Peak at 4.67ppm is the chemical shift of secondary carbon proton connected with ester group；Peak at 5.72ppm is ester group
The chemical shift of connected tertiary carbon proton；Multiplet at 7ppm-8ppm is the chemical shift of phenyl ring and proton on imidazole ring；
The chemical shift of the unimodal secondary carbon proton for being respectively connected with two nitrogen on imidazole ring at 9.17ppm.Meanwhile, which is in 1-
There is signal peak strongly in the range of 1.5ppm, and polyester is then shown in 1-1.5ppm scope with the 1HNMR spectrogram of PIL-Cl
Interior nothing clear signal peak.In addition, all there is the signal corresponding with methyl blue nuclear-magnetism in 7.02ppm, 7.28ppm, 7.54ppm etc.
Peak.This demonstrate that the successful preparation of the poly ion liquid type basic indicator suitable for non-polar solven.
Fig. 2 correspond to embodiment 1 prepare the poly ion liquid type basic indicator suitable for non-polar solven show difference sweep
Retouch calorimetric spectrogram.
Fig. 3 corresponds to the dissolubility of the poly ion liquid type basic indicator suitable for non-polar solven prepared by embodiment 1
Test photo.The bright polymer of the chart does not dissolve in upper strata aqueous phase, and is dissolved only in lower floor's dichloromethane phase.This can be described accordingly
Polymer changes the water solubility of methyl blue completely, then is dissolved in non-polar solven.
The poly ion liquid type basic indicator suitable for non-polar solven that Fig. 4 corresponds to the preparation of embodiment 1 is different in difference
Alkalescence under propylamine concentration indicates photo.The chart is bright when isopropylamine concentration increases to 2.1mol/L from 0mol/L, the polymer
Dichloromethane solution gradually become colorless by blueness.Can illustrate that the polymer has ten in non-polar solven accordingly clearly demarcated
Aobvious alkalescence indicates function.
The poly ion liquid type basic indicator suitable for non-polar solven that Fig. 5 corresponds to the preparation of embodiment 1 is different in difference
Ultraviolet-visible spectrogram under propylamine concentration.The dichloromethane solution of the polymer is maximum during the increase of isopropylamine concentration to be inhaled
Receipts wavelength does not almost change and maintains 590nm or so, and its absorbance then goes out as isopropylamine concentration increases aggregate performance
The trend of reduction, therefore see that solution is become colorless by blueness from naked eyes.
Fig. 6 corresponds to the thermal weight loss of the poly ion liquid type basic indicator suitable for non-polar solven prepared by embodiment 1
Curve.Curve is weightless below 220 DEG C to be less than 10, illustrates that the polymer has preferable heat endurance.
Fig. 7 corresponds to the poly ion liquid type basic indicator suitable for non-polar solven prepared by embodiment 1, example 2, example 3
The molecule measuring test result measured through gel permeation chromatography and corresponding n value.
Claims (10)
1. a kind of poly ion liquid type basic indicator suitable for non-polar solven, it is characterised in that its structural formula is as follows：
Wherein, n is 10-50.
2. the preparation method of the poly ion liquid type basic indicator suitable for non-polar solven described in claim 1, its are special
Levy and be, comprise the following steps：
Step a：Eliminating water deoxygenation process is carried out to reaction vessel；
Step b：Phthalic anhydride and DMF are added in reaction vessel under nitrogen protection, and stirring is obtained
The DMF solution of phthalic anhydride；
Step c：Second two is added in the DMF solution of the phthalic anhydride in step b under nitrogen protection
Alcohol, stirring；
Step d：Epoxychloropropane is added in the solution that step c is obtained, is reacted under agitation；
Step e：Remaining epoxychloropropane in the mixture for obtaining is reacted in removing step d, adds N- methylimidazole, in stirring
Under reacted；
Step f：The mixture that obtains will be reacted add in acetone in step e, stirring, separation of solid and liquid are precipitated；
Step g：The precipitation obtained in step f is dissolved in deionized water, is added drop-wise in the methyl blue aqueous solution, enters under agitation
Row reaction, separation of solid and liquid are precipitated；
Step h：The precipitate with deionized water obtained in step g is rinsed repeatedly, vacuum drying, be added in dichloromethane, stir
Mix to form mixture；
Step i：The mixture obtained in step h is filtered, filtrate is obtained, rotary evaporation removes dichloromethane solvent, vacuum is done
Dry, obtain the poly ion liquid type basic indicator suitable for non-polar solven.
3. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step c, it is 1%-2% that described ethylene glycol accounts for the mole percent of phthalic anhydride.
4. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step d, described epoxychloropropane is 1-1.3 with the mol ratio of phthalic anhydride:1.
5. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step d, is reacted under described stirring, its temperature is 95-120 DEG C, its reaction time is 10-
12 hours.
6. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, N, the N- dimethyl formyl of the phthalic anhydride in the N- methylimidazole added in described step e and step b
The mol ratio of the phthalic anhydride in amine aqueous solution is 1.1-1.5:1.
7. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step e, reacted under the stirring, its reaction temperature is 80-95 DEG C, and its reaction time is 4-6
My god.
8. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step f, the volume ratio of the mixture obtained in the acetone and step e is 9-13:1.
9. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step g, the methyl blue with the mol ratio of TMSIM N imidazole group in gained precipitation in step f is
1.2-1.8:1.
10. the preparation method of the poly ion liquid type basic indicator of non-polar solven is applied to as claimed in claim 2, its
It is characterised by, in described step g, reacted under the stirring, its reaction temperature is 5-25 DEG C, and its reaction time is 10-
20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493337.5A CN105131271B (en) | 2015-08-12 | 2015-08-12 | Poly ion liquid type basic indicator and its preparation suitable for non-polar solven |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510493337.5A CN105131271B (en) | 2015-08-12 | 2015-08-12 | Poly ion liquid type basic indicator and its preparation suitable for non-polar solven |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105131271A CN105131271A (en) | 2015-12-09 |
| CN105131271B true CN105131271B (en) | 2017-03-08 |
Family
ID=54716880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510493337.5A Expired - Fee Related CN105131271B (en) | 2015-08-12 | 2015-08-12 | Poly ion liquid type basic indicator and its preparation suitable for non-polar solven |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105131271B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108676173B (en) * | 2018-05-18 | 2020-12-18 | 东华大学 | Polyion liquid with ionic bond as framework and preparation method thereof |
| CN114018906B (en) * | 2021-09-28 | 2024-03-12 | 神美科技有限公司 | Test paper for detecting nitrite content and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199280A (en) * | 2011-04-08 | 2011-09-28 | 浙江大学 | Fluoro-polyester resin and preparation method and application thereof |
| CN104151535B (en) * | 2014-08-09 | 2016-04-27 | 河北工业大学 | A kind of polyester block copolymer and preparation method thereof |
-
2015
- 2015-08-12 CN CN201510493337.5A patent/CN105131271B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105131271A (en) | 2015-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Polyelectrolyte complex/PVA membranes for diffusion dialysis | |
| CN105199090B (en) | It is applicable to poly ion liquid type acid indicator and the preparation thereof of non-polar solven | |
| CN103261279B (en) | Quaternised polybenzimidazole | |
| CN109678143B (en) | Hyperbranched rare earth phthalocyanine modified graphene oxide, preparation method thereof and application thereof in laser protection | |
| Ogoshi et al. | Pillar [5] arene-based nonionic polyrotaxanes and a topological gel prepared from cyclic host liquids | |
| CN105131271B (en) | Poly ion liquid type basic indicator and its preparation suitable for non-polar solven | |
| CA2412818A1 (en) | Conductive polymeric compositions for lithium batteries | |
| CN109734930B (en) | Preparation method and application of acid-responsive color-changing material | |
| CN104844764B (en) | A kind of alkaline anion-exchange membrane and preparation method thereof | |
| CN102643421A (en) | Novel polymer containing phosphonate group and preparation method and application of novel polymer | |
| CN102634010A (en) | Polymers containing phosphoric acid group and salts thereof, and preparation method and application thereof | |
| CN105199091B (en) | It is applicable to poly ion liquid type acid-base indicator and the preparation thereof of non-polar solven | |
| CN106255715A (en) | The ionene that hydroxide is stable | |
| CN108997542A (en) | A kind of preparation method and applications of amphiphilic temperature sensitive block polymer | |
| CN104276936A (en) | Bis-pyrene compound and fluorescent nano-aggregate thereof and application of fluorescent nano-aggregate | |
| CN105348512B (en) | A kind of polyarylether material containing acid imide side base and preparation method thereof | |
| CN106749079B (en) | The amide electrolyte preparation method of diamines containing benzoxazoles and application | |
| CN104829813B (en) | A kind of ionomeric polymer containing phosphine, preparation method and anion-exchange membrane | |
| CN101862606B (en) | Polymer separation membrane and preparation method | |
| CN101701052B (en) | Nitrated cellulose grafted by spirooxazine group and preparation method thereof | |
| CN102430344A (en) | Hollow polyvinylidene fluoride fibrous membrane and preparation method as well as application thereof | |
| CN108424679B (en) | Polymer coating with infrared optical characteristic and containing bimetal coordination, preparation method and application thereof | |
| US10249403B2 (en) | P(CN)3 reactions with lithium dicynamide producing metalated carbon phosphonitride extended solids | |
| US8931114B2 (en) | Elastomeric composites with tether-containing, conducting polymers for nanoscale diffusion control | |
| CN109810507A (en) | A kind of preparation method of polyphenylene sulfide/ferriferrous oxide composite material |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 Termination date: 20190812 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |