CN109608642A - Polysiloxanes ionic liquid and preparation method thereof - Google Patents
Polysiloxanes ionic liquid and preparation method thereof Download PDFInfo
- Publication number
- CN109608642A CN109608642A CN201811509614.7A CN201811509614A CN109608642A CN 109608642 A CN109608642 A CN 109608642A CN 201811509614 A CN201811509614 A CN 201811509614A CN 109608642 A CN109608642 A CN 109608642A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- polysiloxanes
- reaction
- alkyl
- dimethoxysilane
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
Abstract
The present invention relates to a kind of polysiloxanes ionic liquids and preparation method thereof, and this method comprises the following steps: halogenated alkyl dimethoxysilane and 1- alkyl imidazole being reacted, imidazolium halide ionic liquid is obtained；Polymerization reaction is hydrolyzed under acid condition in the imidazolium halide ionic liquid, obtains polysiloxanes ionic liquid.So first pass through halogenated alkyl dimethoxysilane and the reaction of 1- alkyl imidazole, obtain the imidazolium halide ionic liquid small molecule with imidazoles base, hydrolysis-polymerization reaction is occurred using the imidazolium halide ionic liquid small molecule with imidazoles base, it can make on the imidazolium halide ionic liquid monomer of per molecule with imidazoles functional group, and then reaction is promoted to tend to be complete, obtain the higher product of purity, it so avoids incomplete using the biggish polymer of molecule and imidazoles functional group graft reaction, cause product impure, impurity not can be removed the problem for causing product purity lower, to improve the purity of product.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of polysiloxanes ionic liquid and its preparation side
Method.
Background technique
Ion liquid polymer is the high molecular polymer with ionic liquid structure, has both ionic liquid and polymer
The advantages of electrolyte, such as with wider liquid temperature range, preferable electrical conductance, can be used as ion liquid polymer electrolysis
Matter, such as it is as catalyst, with better catalytic performance；Additionally due to the form of diverse of polymer can for example fall from liquid
Solid or elastomer, therefore the functionalization of ion liquid polymer is enriched, so that ion liquid polymer is with great
Designability.However at present there is reaction not exclusively in the practical synthesis technology of ion liquid polymer, and then lead to product purity
Lower problem.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of higher polysiloxanes ionic liquid of purity, correspondingly also mention
Its polysiloxanes ionic liquid obtained is supplied.
A kind of polysiloxanes ionic liquid has the following structure formula (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X-For halide anion, PF6 -Or BF4 -。
Above-mentioned polysiloxanes ionic liquid is linear type polysiloxanes, while having the characteristic of good ionic liquid, is had
There is higher conductivity, and fusing point is lower, can be used as polyelectrolyte.
R in one of the embodiments,1、R2For methyl；Y is 1~3.
Y is 3 in one of the embodiments,；X-For F-、Cl-、Br-、PF6 -Or BF4 -。
A kind of preparation method of polysiloxanes ionic liquid, includes the following steps:
Halogenated alkyl dimethoxysilane and 1- alkyl imidazole are reacted, imidazolium halide ionic liquid is obtained；
Polymerization reaction is hydrolyzed under acid condition in the imidazolium halide ionic liquid, obtains polysiloxanes ion
Liquid；
Wherein, the halogenated alkyl dimethoxysilane, the 1- alkyl imidazole, the imidazolium halide ionic liquid and
The structural formula of the polysiloxanes ionic liquid is respectively as shown in (I), (II), (III) and (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X1For halogen atom；X-For halide anion.
R in one of the embodiments,1、R2For methyl；Y is 1~3；X-For F-、Cl-Or Br-。
The condition of the halogenated alkyl dimethoxysilane and 1- alkyl imidazole reaction in one of the embodiments,
For in 105 DEG C~115 DEG C reaction 15h~20h；
The condition of the hydrolytic-polymeric reaction is in 60 DEG C~70 DEG C reaction 15h~20h.
A kind of preparation method of polysiloxanes ionic liquid, includes the following steps:
Halogenated alkyl dimethoxysilane and 1- alkyl imidazole are reacted, imidazolium halide ionic liquid is obtained；
The imidazolium halide ionic liquid and hexafluorophosphoric acid anion or fluoboric acid anion progress ion exchange is anti-
It answers, the imidazolium ionic liquid after obtaining ion exchange；
Polymerization reaction is hydrolyzed under acid condition in imidazolium ionic liquid after the ion exchange, obtains poly- silicon
Oxygen alkane ionic liquid；
Wherein, the halogenated alkyl dimethoxysilane, the 1- alkyl imidazole, the imidazolium halide ionic liquid and
The structural formula of the polysiloxanes ionic liquid is respectively as shown in (I), (II), (III) and (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X1For halogen atom；X-For PF6 -Or BF4 -。
R in one of the embodiments,1、R2For methyl；Y is 1~3.
The condition of the halogenated alkyl dimethoxysilane and 1- alkyl imidazole reaction in one of the embodiments,
For in 105 DEG C~115 DEG C reaction 15h~20h；
The condition of the hydrolytic-polymeric reaction is in 60 DEG C~70 DEG C reaction 15h~20h.
The condition of the ion-exchange reactions is in 60 DEG C~70 DEG C reaction 3h~5h in one of the embodiments,.
The preparation method of above-mentioned polysiloxanes ionic liquid, first passes through halogenated alkyl dimethoxysilane and 1- alkyl imidazole
Reaction, obtains the imidazolium halide ionic liquid small molecule with imidazoles base, using having the function of the halogenation miaow of imidazoles base
Hydrolysis-polymerization reaction occurs for azoles ionic liquid small molecule, can make equal band on the imidazolium halide ionic liquid monomer of per molecule
There is imidazoles functional group, and then reaction is promoted to tend to completely, obtain the higher product of purity, so avoid larger using molecule
Polymer and imidazoles functional group graft reaction it is incomplete, cause product is impure, impurity not can be removed cause product purity compared with
Low problem, to improve the purity of product.
In addition, the preparation method of above-mentioned polysiloxanes ionic liquid is not necessarily to through other linking groups, it can be by imidazoles function
Energy group is connected on silane, is advantageously formed without other heteroatomic polysiloxanes ionic liquids.
Detailed description of the invention
Fig. 1 is the infrared spectrum of imidazolitm chloride ionic liquid made from embodiment 1；
Fig. 2 is the infrared spectrum of polysiloxanes ionic liquid made from embodiment 1；
Fig. 3 is the infrared spectrum of polysiloxanes ionic liquid made from embodiment 2；
Fig. 4 is the uv absorption spectra of imidazolitm chloride ionic liquid made from embodiment 1；
Fig. 5 is the uv absorption spectra of polysiloxanes ionic liquid made from embodiment 1；
Fig. 6 is the nuclear magnetic spectrum of imidazolium halide ionic liquid made from embodiment 1.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The present invention provides the polysiloxanes ionic liquids of an embodiment, have the following structure formula (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X-For halide anion, PF6 -Or BF4 -。
R in one of the embodiments,1、R2For methyl；Y is 1~3.
Y is 3 in one of the embodiments,；X-For F-、Cl-、Br-、PF6 -Or BF4 -。
In a specific example, the structural formula of polysiloxanes ionic liquid is as follows:
Above-mentioned polysiloxanes ionic liquid is linear type polysiloxanes, while having the characteristic of fine ionic liquid, is had
Higher conductivity, and fusing point is lower, can be used as polyelectrolyte.Preferably, X-For Cl-、PF6 -Or BF4 -.It is highly preferred that X-For
PF6 -Or BF4 -, with lower fusing point, the characteristic of good ionic liquid.
The present invention also provides the preparation methods of any one of the above polysiloxanes ionic liquid, include the following steps S11
~S12:
Step S11: halogenated alkyl dimethoxysilane and 1- alkyl imidazole are reacted, imidazolium halide salt ion liquid is obtained
Body.
Step S12: polymerization reaction is hydrolyzed under acid condition in imidazolium halide ionic liquid, obtains polysiloxanes
Ionic liquid.
Wherein, halogenated alkyl dimethoxysilane, 1- alkyl imidazole, imidazolium halide ionic liquid and polysiloxanes ion
The structural formula of liquid is respectively as shown in (I), (II), (III) and (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X1For halogen atom；X-For halide anion.
R in one of the embodiments,1、R2For methyl；Y is 1~3；X-For F-、Cl-Or Br-。
In a specific example, the structural formula of polysiloxanes ionic liquid is as follows:
It is understood that anion can be substituted for other by ion exchange in polysiloxanes ionic liquid made from step S12
Anion, such as halide anion and PF6 -Or BF4 -Between be replaced mutually, or mutually replacing between different halide anion
It changes.
Halogenated alkyl dimethoxysilane and the condition of 1- alkyl imidazole reaction are in 105 in one of the embodiments,
DEG C~115 DEG C of reaction 15h~20h；Further, the reaction is using the organic solvents such as toluene, stratification after reaction, under separation
Layer gel, obtains imidazolium halide ionic liquid.
The condition of hydrolytic-polymeric reaction is in 60 DEG C~70 DEG C reaction 15h~20h in one of the embodiments,.Into one
Step ground, hydrolytic-polymeric reaction can carry out under the acidic catalysis conditions of corresponding HX, such as HCl.Further, poly- silicon is being made
After oxygen alkane ionic liquid, further include the steps that being dissolved in reheating evaporation water in water, so that hydrolysis and polymerization reaction are into one
Step is complete.
The present invention also provides the preparation methods of any one of the above polysiloxanes ionic liquid, include the following steps S21
~S23:
Step S21: halogenated alkyl dimethoxysilane and 1- alkyl imidazole are reacted, imidazolium halide salt ion liquid is obtained
Body.
Step S21 is identical with step S11.Halogenated alkyl dimethoxysilane and 1- alkyl in one of the embodiments,
The condition of imidazoles reaction is in 105 DEG C~115 DEG C reaction 15h~20h；Further, which uses the organic solvents such as toluene,
Stratification after reaction separates lower layer's gel, obtains imidazolium halide ionic liquid.
Step S22: imidazolium halide ionic liquid and hexafluorophosphoric acid anion or fluoboric acid anion are subjected to ion friendship
Change reaction, the imidazolium ionic liquid after obtaining ion exchange.
Compared to above-mentioned preparation method, the ion-exchange reactions step is increased before step 23 hydrolytic-polymeric reaction, it will
Halide anion is substituted for hexafluorophosphoric acid anion or fluoboric acid anion, the imidazolium ion after the obtained ion exchange
Since the structure of anion is larger, the effect between cation reduces liquid, therefore its fusing point is relatively low, and then available
Better ionic liquid performance.
The condition of ion-exchange reactions is in 60 DEG C~70 DEG C reaction 3h~5h in one of the embodiments,.Further
Ground, ion-exchange reactions can carry out in the organic solvents such as methanol.Further, hexafluorophosphoric acid anion or fluoboric acid anion
It can be provided by corresponding salt, such as NaPF6Or NaBF4。
Step S23: by the imidazolium ionic liquid after ion exchange in hydrolyzed under acidic conditions, polysiloxanes ion is obtained
Liquid.
The condition of hydrolytic-polymeric reaction is in 60 DEG C~70 DEG C reaction 15h~20h in one of the embodiments,.Into one
Step ground, hydrolytic-polymeric reaction can carry out under the acidic catalysis conditions of corresponding HX, such as fluoboric acid.Further, it is being made
After polysiloxanes ionic liquid, further include the steps that being dissolved in reheating evaporation water in water, so that hydrolysis and polymerization reaction
Further completely.
Wherein, halogenated alkyl dimethoxysilane, 1- alkyl imidazole, imidazolium halide ionic liquid and polysiloxanes ion
The structural formula of liquid is respectively as shown in (I), (II), (III) and (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X1For halogen atom；X-For PF6 -Or BF4 -。
R in one of the embodiments,1、R2For methyl；Y is 1~3.
In a specific example, the structural formula of polysiloxanes ionic liquid is as follows:
It is understood that anion can be substituted for other by ion exchange in polysiloxanes ionic liquid made from step S23
Anion, such as PF6 -Or BF4 -Mutually replacing between being replaced mutually between halide anion, or different halide anions
It changes.
The preparation method of above-mentioned polysiloxanes ionic liquid, first passes through halogenated alkyl dimethoxysilane and 1- alkyl imidazole
Reaction, obtains the imidazolium halide ionic liquid small molecule with imidazoles base, using having the function of the halogenation miaow of imidazoles base
Hydrolysis-polymerization reaction occurs for azoles ionic liquid small molecule, can make equal band on the imidazolium halide ionic liquid monomer of per molecule
There is imidazoles functional group, and then reaction is promoted to tend to completely, obtain the higher product of purity, so avoid larger using molecule
Polymer and imidazoles functional group graft reaction it is incomplete, cause product is impure, impurity not can be removed cause product purity compared with
Low problem, to improve the purity of product.
In addition, the preparation method of above-mentioned polysiloxanes ionic liquid is not necessarily to through other linking groups, it can be by imidazoles function
Energy group is connected on silane, is advantageously formed without other heteroatomic polysiloxanes ionic liquids.
The following are specific embodiments.
Embodiment 1
(1) preparation of imidazolium halide ionic liquid
18.5g γ-chloropropyl dimethoxysilane and 10g methylimidazole and 30mL first are added in 250mL three-necked bottle
Benzene, solution are in yellow, and first pre- stirring is uniformly mixed it, and oil bath temperature control heats and is stirred to react 18h at about 110 DEG C, and color becomes
Brown color.It standing to being layered, upper layer is clear yellow solution, and lower layer is brown yellow gel, lower layer's gel is separated with separatory funnel,
Obtain imidazolium chloride salt ionic liquid.
(2) ion-exchange reactions
The preparation of tetrafluoroborate imidazole ion liquid
3.75 grams of imidazolitm chloride ionic liquids and 1.5 grams of NaBF4 powder are taken (to be dissolved in 30mL by mole mass ratio 1:1)
In methanol, liquid is glassy yelloe, and solution becomes muddy milky after starting stirring, and solution becomes clarification later, and it is small to be heated to reflux 4
When, oil bath temperature control heats about 65 DEG C, generates a small amount of white precipitate.Upper solution is tetrafluoroborate imidazole ion liquid, precipitating
For NaCl.
(3) hydrolytic-polymeric reaction
After ion exchange, supernatant is taken out, 2mL fluoboric acid is added, oil bath temperature control heats about 65 DEG C, is heated to reflux 18h,
Solution is clear, yellowish solution.After change reflux unit be distilling apparatus, that is, steam extra methanol solvate, obtain white solid
And oily mixture, wherein white solid (excessive fluoboric acid) is dissolved in water and grease is insoluble.By mixture it is soluble in water to
After fully reacting, the extra moisture of heating evaporation obtains polysiloxanes ionic liquid.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that, step (2) ion-exchange reactions: prepare hexafluoro phosphorus
Hydrochlorate imidazole ion liquid；
Preparing for hexafluorophosphate imidazole ion liquid is as follows: taking 5 grams of imidazolitm chloride ionic liquids and 3.3 grams of KPF6 powder
End (pressing mole mass ratio 1:1) is dissolved in 80mL methanol, and liquid is glassy yelloe, and solution becomes muddy milky white after starting stirring
Color, solution becomes clarification later, is heated to reflux 4 hours, and oil bath temperature control heats about 65 DEG C, generates a small amount of white precipitate.Upper solution
For hexafluorophosphate imidazole ion liquid, it is precipitated as NaCl.
The chemical equation of polysiloxanes ionic liquid made from the step of embodiment 2 (3) is as follows:
In the step of embodiment 1 and embodiment 2 (1), solution layering, it was demonstrated that reaction produces the biggish ionic liquid of polarity
It is immiscible with the lesser toluene of polarity.And the upper solution separated after reacting is dissolved each other with toluene, it was demonstrated that is solvent toluene.By lower layer
Gel is cleaned three times with toluene, and thin-layer chromatography is done together with raw material, and the point climbed is inconsistent, further proves not to be raw material,
Reaction.Polysiloxanes ionic liquid made from Example 1~2 does thin-layer chromatography again, has 1 point in thin plate, it was demonstrated that product is pure
Only.
FIG. 1 to FIG. 3 is respectively imidazolitm chloride ionic liquid made from 1 step of embodiment (1), made from Examples 1 to 2
The infrared spectrum of polysiloxanes ionic liquid.
As can be known from Fig. 1,3138cm-1And 3080cm-1It is the C-H stretching vibration peak on imidazole ring, 2939cm in figure-1It is
CH on imidazole side chain3 -Stretching vibration peak, 1631cm in figure-1With 1562cm-1, it is the skeletal vibration of imidazole ring, in figure
1165cm-1It is imidazole ring C-H in-plane bending vibration peak, 1074cm-1It is the characteristic absorption peak of Si-O-C.From spectrogram above
Can determine and contain imidazole radicals in the substance, and contain silicon oxygen bond, can preliminary proof γ-chloropropyl dimethoxysilane and first
The reaction of base imidazoles, forms ionic liquid.
As can be known from Fig. 2,3149cm-1Two peaks of left and right are the C-H stretching vibration peak on imidazole ring, 2972cm in figure-1
It is CH on imidazole side chain3Stretching vibration peak, 1631cm in figure-1With 1562cm-1It is the skeletal vibration of imidazole ring, in figure
771cm-1Place is the stretching vibration peak of B-F.The 1085cm in figure unlike the unpolymerized imidazole ion liquid in front-1Place has
Wider peak, this is the peak that the Si-O-Si of linear type skeleton is formed, and illustrates that the Si-O key in raw material is formd by hydrolytic condensation
Si-O-Si skeleton forms regular linear structure.It can be seen, imidazolitm chloride ionic liquid with BF4-
Ion exchange has been carried out, and has formd linear paradigmatic structure.In addition, being respectively present 3419cm in two figures-1And 3431cm-1Characteristic absorption peak, it may be possible to since the water in ionic liquid is not completely removed, there is the characteristic absorption band of O-H.
The main peak of Fig. 3 and Fig. 2 is essentially identical, and main difference is in 746cm-1The PF at place6 -The flexible vibration of the P-H key of formation
It is dynamic.
Fig. 4~Fig. 5 is poly- silicon oxygen made from imidazolitm chloride ionic liquid made from 1 step of embodiment (1) and embodiment 1
The uv absorption spectra of alkane ionic liquid.From in Fig. 4~Fig. 5 it is found that there is strong absworption peak at 230nm, it was demonstrated that have imidazoles
Group exists.
The specific method is as follows for the measurement of conductivity: with the conductivity of pure water as a comparison, measuring secondary distilled water at room temperature
Conductivity be 0.034ms/cm.
1) raw material of embodiment 1: γ-chloropropyl dimethoxysilane conductance measurement
42.5919g grams of secondary distilled water is weighed with electronic balance, 0.2169g γ-chloropropyl dimethoxysilane is added,
Measuring its conductivity is 0.123ms/cm.
2) conductance measurement of imidazolitm chloride ionic liquid made from 1 step of embodiment (1)
42.4158g secondary distilled water is weighed with electronic balance, 0.2282g imidazolitm chloride ionic liquid is added, measures it
Conductivity is 2.452ms/cm.
3) conductance measurement of tetrafluoroborate imidazole ion liquid made from 1 step of embodiment (2)
40.5711g secondary distilled water is weighed with electronic balance, 0.1980g tetrafluoroborate imidazolium ionic liquid is added,
Measuring its conductivity is 0.750ms/cm.
4) conductance measurement of polysiloxanes ionic liquid made from 1 step of embodiment (3)
41.1400g secondary distilled water is weighed with electronic balance, 0.0205g polysiloxanes ionic liquid is added, measures its electricity
Conductance is 1.4607ms/cm.
The calculating calculation formula of unit mass concentration conductivity: K=G × J；C=M1/M2×ρ2；G=G '/C；
It is 1.0, K is conductivity that wherein J, which is electrolytic cell constant, and G is conductance, and G ' is the conductivity measured, and C is the matter of solute
Measure concentration, M1By survey substance quality, M2For the quality of pure water, ρ2For the density of water.
It is measured according to above formula:
1. γ-chloropropyl dimethoxysilane unit mass concentration conductivity 24.1531ms/cm；
2. the unit mass concentration conductivity of imidazolitm chloride ionic liquid is 455.7621ms/cm；
3. the unit mass concentration conductivity of tetrafluoroborate imidazole ion liquid is 153.6885ms/cm；
4. the unit mass concentration conductivity of the polysiloxanes ionic liquid of embodiment 1 is 2931.3667ms/cm.
It follows that pure water is almost non-conductive, the conductivity of raw material is also very low, can be seen that and original from result above
Material is greatly improved compared to the conductivity of solution after reaction, illustrates the presence for having a large amount of ions in the liquid, shape in solution
At ionic liquid.After ion liquid polymer is made in ionic liquid, conductivity is even more to be improved, and illustrates polysiloxanes
Ionic liquid has good electric conductivity.
Imidazolium halide ionic liquid made from embodiment 1 is subjected to carbon-13 nmr spectra detection, obtains nuclear magnetic spectrum such as
Shown in Fig. 6, as can be known from Fig. 6, imidazolium halide ionic liquid made from 1 step of embodiment (1) is consistent with its structural formula.Due to
Polysiloxanes ionic liquid made from embodiment 1 and embodiment 2 is polymer, therefore can not detect its nuclear magnetic spectrum, the present invention
Mainly characterized by above-mentioned infared spectrum and ultra-violet absorption spectrum.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of polysiloxanes ionic liquid, which is characterized in that have the following structure formula (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X-For halide anion, PF6 -Or BF4 -。
2. polysiloxanes ionic liquid as described in claim 1, which is characterized in that R1、R2For methyl；Y is 1~3.
3. polysiloxanes ionic liquid as claimed in claim 2, which is characterized in that y 3；X-For F-、Cl-、Br-、PF6 -Or
BF4 -。
4. a kind of preparation method of polysiloxanes ionic liquid, which comprises the steps of:
Halogenated alkyl dimethoxysilane and 1- alkyl imidazole are reacted, imidazolium halide ionic liquid is obtained；
Polymerization reaction is hydrolyzed under acid condition in the imidazolium halide ionic liquid, obtains polysiloxanes ionic liquid
Body；
Wherein, the halogenated alkyl dimethoxysilane, the 1- alkyl imidazole, the imidazolium halide ionic liquid and described
The structural formula of polysiloxanes ionic liquid is respectively as shown in (I), (II), (III) and (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X1For halogen atom；X-For halide anion.
5. the preparation method of polysiloxanes ionic liquid as claimed in claim 4, which is characterized in that R1、R2For methyl；Y is 1
~3；X-For F-、Cl-Or Br-。
6. the preparation method of polysiloxanes ionic liquid as described in claim 4 or 5, which is characterized in that the halogenated alkyl
Dimethoxysilane and the condition of 1- alkyl imidazole reaction are in 105 DEG C~115 DEG C reaction 15h~20h；
The condition of the hydrolytic-polymeric reaction is in 60 DEG C~70 DEG C reaction 15h~20h.
7. a kind of preparation method of polysiloxanes ionic liquid, which comprises the steps of:
Halogenated alkyl dimethoxysilane and 1- alkyl imidazole are reacted, imidazolium halide ionic liquid is obtained；
The imidazolium halide ionic liquid and hexafluorophosphoric acid anion or fluoboric acid anion are subjected to ion-exchange reactions, obtained
Imidazolium ionic liquid after to ion exchange；
Polymerization reaction is hydrolyzed under acid condition in imidazolium ionic liquid after the ion exchange, obtains polysiloxanes
Ionic liquid；
Wherein, the halogenated alkyl dimethoxysilane, the 1- alkyl imidazole, the imidazolium halide ionic liquid and described
The structural formula of polysiloxanes ionic liquid is respectively as shown in (I), (II), (III) and (IV):
Wherein, R1、R2For alkyl；Y is positive integer；N is the degree of polymerization；X1For halogen atom；X-For PF6 -Or BF4 -。
8. the preparation method of polysiloxanes ionic liquid as claimed in claim 7, which is characterized in that R1、R2For methyl；Y is 1
~3.
9. the preparation method of polysiloxanes ionic liquid as claimed in claim 7 or 8, which is characterized in that the halogenated alkyl
Dimethoxysilane and the condition of 1- alkyl imidazole reaction are in 105 DEG C~115 DEG C reaction 15h~20h；
The condition of the hydrolytic-polymeric reaction is in 60 DEG C~70 DEG C reaction 15h~20h.
10. the preparation method of polysiloxanes ionic liquid as claimed in claim 7 or 8, which is characterized in that the ion exchange
The condition of reaction is in 60 DEG C~70 DEG C reaction 3h~5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811509614.7A CN109608642A (en) | 2018-12-11 | 2018-12-11 | Polysiloxanes ionic liquid and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811509614.7A CN109608642A (en) | 2018-12-11 | 2018-12-11 | Polysiloxanes ionic liquid and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109608642A true CN109608642A (en) | 2019-04-12 |
Family
ID=66007674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811509614.7A Pending CN109608642A (en) | 2018-12-11 | 2018-12-11 | Polysiloxanes ionic liquid and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109608642A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1382630A1 (en) * | 2002-07-17 | 2004-01-21 | Goldschmidt AG | Process for the production of organically modified Polysiloxanes by using ionic liquids |
| JP2009286699A (en) * | 2008-05-27 | 2009-12-10 | Kri Inc | Ionic liquid containing organic and inorganic polymerizable functional groups and its high molecular ionic compound |
| CN103706341A (en) * | 2013-12-19 | 2014-04-09 | 武汉大学 | Ionic liquid bonded polysiloxane stationary phase and preparation method thereof |
| CN104231274A (en) * | 2014-08-21 | 2014-12-24 | 中国日用化学工业研究院 | Surface activity organosilicon room-temperature ionic liquid and synthetic method thereof |
| CN104371110A (en) * | 2014-10-14 | 2015-02-25 | 中国水产科学研究院黄海水产研究所 | Ionic liquid polymer for extracting floxacin compounds, and preparation method and application thereof |
| CN105130902A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of ionic liquid |
| KR101737434B1 (en) * | 2015-10-22 | 2017-05-18 | 한국과학기술연구원 | Ionic polyhedral oligomeric silsesquioxane, electrolyte composition for secondary battery including the same, polymer electrolyte for secondary battery and method of manufacturing the same |
| CN108164707A (en) * | 2018-01-08 | 2018-06-15 | 济南大学 | A kind of novel fluorescence polysiloxane group ionic liquid and its application |
-
2018
- 2018-12-11 CN CN201811509614.7A patent/CN109608642A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1382630A1 (en) * | 2002-07-17 | 2004-01-21 | Goldschmidt AG | Process for the production of organically modified Polysiloxanes by using ionic liquids |
| JP2009286699A (en) * | 2008-05-27 | 2009-12-10 | Kri Inc | Ionic liquid containing organic and inorganic polymerizable functional groups and its high molecular ionic compound |
| CN103706341A (en) * | 2013-12-19 | 2014-04-09 | 武汉大学 | Ionic liquid bonded polysiloxane stationary phase and preparation method thereof |
| CN104231274A (en) * | 2014-08-21 | 2014-12-24 | 中国日用化学工业研究院 | Surface activity organosilicon room-temperature ionic liquid and synthetic method thereof |
| CN104371110A (en) * | 2014-10-14 | 2015-02-25 | 中国水产科学研究院黄海水产研究所 | Ionic liquid polymer for extracting floxacin compounds, and preparation method and application thereof |
| CN105130902A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of ionic liquid |
| KR101737434B1 (en) * | 2015-10-22 | 2017-05-18 | 한국과학기술연구원 | Ionic polyhedral oligomeric silsesquioxane, electrolyte composition for secondary battery including the same, polymer electrolyte for secondary battery and method of manufacturing the same |
| CN108164707A (en) * | 2018-01-08 | 2018-06-15 | 济南大学 | A kind of novel fluorescence polysiloxane group ionic liquid and its application |
Non-Patent Citations (6)
| Title |
|---|
| QING QUAN WEI等: "A novel ionic liquids grafted polysiloxane for capillary gas chromatography", 《CHINESE CHEMICAL LETTERS》 * |
| QINGQUAN WEI等: "Separation Characteristics of Ionic Liquids Grafted Polymethylsiloxanes Stationary Phases for Capillary GC", 《CHROMATOGRAPHIA》 * |
| TAKUYA KUBO等: "Preparation of Imidazolium Salt Type Ionic Liquids Containing Cyclic Siloxane Frameworks", 《CHEM. LETT.》 * |
| 大连工学院等: "《合成橡胶工艺学》", 31 July 1961, 中国工业出版社 * |
| 杨显万等: "《湿法冶金》", 30 April 1998, 冶金工业出版社 * |
| 柳云骐等: "《材料化学》", 28 February 2013, 中国石油大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Atanasov et al. | Highly phosphonated polypentafluorostyrene | |
| CN1867614B (en) | Phosphonic-acid grafted hybrid inorganic-organic proton electrolyte membranes (PEMs) | |
| Çelik et al. | Preparation and proton conductivity of acid-doped 5-aminotetrazole functional poly (glycidyl methacrylate) | |
| Bartels et al. | Synthesis, morphology, and ion conduction of polyphosphazene ammonium iodide ionomers | |
| Ataollahi et al. | A polyketone-based anion exchange membrane for electrochemical applications: Synthesis and characterization | |
| Yue et al. | Proton transport pathways in an acid–base complex consisting of a phosphonic acid group and a 1, 2, 3-triazolyl group | |
| Womble et al. | Rapid analysis of tetrakis (dialkylamino) phosphonium stability in alkaline media | |
| Liu et al. | Synthesis, characterization, and functionalization of tetrafunctional double-decker siloxanes | |
| El Aziz et al. | Facile synthesis of novel functionalized silsesquioxane nanostructures containing an encapsulated fluoride anion | |
| Göktepe et al. | Synthesis and proton conductivity of poly (styrene sulfonic acid)/heterocycle‐based membranes | |
| CN108164707B (en) | Polysiloxane-based ionic liquid and application thereof | |
| EP0446578B1 (en) | Methods for the preparation of silanes and polysilanes | |
| Tanaka et al. | Synthesis of double-decker silsesquioxanes from substituted difluorosilane | |
| WO2005049183A1 (en) | Sulfonic acid group-containing organic-silica composite membrane and method for producing thereof | |
| CN109608642A (en) | Polysiloxanes ionic liquid and preparation method thereof | |
| WO2017090346A1 (en) | Silicon-containing sulfonate | |
| CN109627443A (en) | Figure polysiloxanes ionic liquid and preparation method thereof | |
| CN109517176A (en) | Silsesquioxane ionic liquid and preparation method thereof | |
| Amarasekara et al. | Synthesis and characterization of polymeric ionic liquid poly (imidazolium chloride-1, 3-diylbutane-1, 4-diyl) | |
| CN110396187B (en) | Preparation method of imidazole polyion liquid | |
| Sgreccia et al. | Stimuli-responsive amphoteric ion exchange polymers bearing carboxylic and amine groups grafted to a cross-linkable silica network | |
| Zheng et al. | Synthesis and ionic conductivity of a novel ionic liquid polymer electrolyte | |
| Ates et al. | Copolymer formation of 9-(2-(benzyloxy) ethyl)-9 H-carbazole and 1-tosyl-1 H-pyrrole coated on glassy carbon electrode and electrochemical impedance spectroscopy | |
| CN104844785B (en) | A kind of cationic polymer, preparation method and anion-exchange membrane, preparation method | |
| CN112703219A (en) | Polyether compound and gas separation membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190412 |
|
| RJ01 | Rejection of invention patent application after publication |