CN101422744A - Ion super strong acid and synthesis method thereof - Google Patents
Ion super strong acid and synthesis method thereof Download PDFInfo
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- CN101422744A CN101422744A CNA2008102337014A CN200810233701A CN101422744A CN 101422744 A CN101422744 A CN 101422744A CN A2008102337014 A CNA2008102337014 A CN A2008102337014A CN 200810233701 A CN200810233701 A CN 200810233701A CN 101422744 A CN101422744 A CN 101422744A
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- strong acid
- product
- super strong
- solvent
- imidazoles
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Abstract
The invention relates to an ionic super acid and a synthesizing method thereof. The invention further relates to a novel material as right; wherein, R is heavy polymer radical such as PE-(CF2)n, wherein, (n is less than or equal to 8), Y is negative ions such as BF4<->, PF6<->, Tf2N<->((CF3SO2)2N<->), TA<->(CF3COO<->), NO3<-> and EtSO4<->, etc. The novel material has performance of super acids and ionic liquids as well as properties of surface active agents. The invention relates to a preparation method of the novel material, which comprises the linking of a -(CF2)nSO3H radical on imidazole ring and the dense covalent coupling of multiple typical ionic liquid radicals with heavy polymer. The ionic super acid compound has certain properties of super acids and ionic liquids as well as specific performance, thus being a potential material and catalyst with specific effects.
Description
Affiliated technical field
The present invention relates to a kind of new material and preparation method thereof.This material had both had some super acids performance and ion liquid characteristic, showed some surfactant properties again.
Background technology
Super acids is the acid stronger than strong acid, and Hami of 100% sulfuric acid special constant Ho value is-11.92, and the Ho value of super acids can reach-12～-20, and acidity can reach 1,000,000,000 times of 100% sulfuric acid.Therefore, they are very competent to the positively ionized of organic compound, but under household condition the organifying compound reacts, even saturated hydrocarbons is at room temperature reacted.Therefore in petroleum refinings such as hydrocarbon cracking, reformation, isomeries, and use in a series of essential industry processes such as petrochemical industry such as olefin hydration, olefinic polymerization, alkylating aromatic hydrocarbon, aromatic hydrocarbons acyl groupization, alcoholic acid esterification and fine chemistry industry.Be the catalyst of a kind of environmental friendliness, facility, high catalytic performance, replace the harmful and poisonous acid catalyst of environment (as H
2SO
4, HF, AlCl
3, AlBr
3, BF
3Deng) become the requirement of environment and industrial self-growth.
At present, known containing-CF
2SO
3The organic acid of H mainly contains following three classes, and a class is the perfluoro alkane type, as: CF
3(CF
2) nSO
3H[n=1-15] reported in literature all arranged; The 2nd ,-CF
2SO
3H is connected on the phenyl ring, as: RC
6H
4CF
2CF
2SO
3H etc.; The 3rd class is-CF
2SO
3H is connected on resin or the polymer, as: Nafion-H etc.; Reported in literature handle-CF is arranged again recently
2SO
3H is connected on the silica, and these compounds all have the character of super acids.They are widely used in the reaction such as cracking, disproportionation, isomerization, alkylation and petrochemical industry of alkane, and required temperature is lower, and has higher selectivity.
Ionic liquid (ILs) is the organic salt that is in a liquid state under the low temperature (100 ℃), be the liquid of forming by ion purely, general relatively large by specific volume, the relative less inorganic anion with volume of the asymmetric organic cation of structure constitutes, in room temperature or near the material that is in a liquid state under the room temperature, therefore be called ionic liquid at room temperature (RTILs) again.It is non-volatile, be difficult for so explosive, be difficult for oxidation, at the stable existence of energy below 300 ℃, all stable to empty G﹠W, being convenient to operation handles, be easy to reclaim, reusable, the environmental pollution that can avoid a large amount of volatile organic solvents to use bringing and to people's harm, being subjected to people and paying close attention to greatly in organic synthesis, is a kind of desirable " green " organic solvent and catalyst.
The ion liquid cation of current research has four classes: quaternary ammonium alkyl ion [NR
xH
4-x]
+, alkyl quaternary phosphine ion [PR
xH
4-x]
+, 1, the imidazol ion [R that the 3-dialkyl group replaces
1R
3Im]
+, the pyridinium ion [RPy] that the N-alkyl replaces
+Ionic liquid can be divided into two big classes according to anionic difference: a class is halide salt (cation is above four kinds)+AlCl
3(wherein Cl also can be replaced by Br), another kind of to be called as new ionic liquid be that fusing point is 1-methyl-3-ethyl-tetrafluoroborate ([emim] [BF of 12 ℃
4]) the basis on grow up, this class ion is different from AlCl
3Ionic liquid, wherein many kinds are stable to water, air, its cation mostly is the imidazol ion [R that alkyl replaces
1R
3Im]
+But there are shortcomings such as the catalysis scope is narrower.
It is therefore, synthetic that to have the compounds that super acids typical case group contains the ionic liquid architectural feature again be very significant.But there are super acids and ion liquid some character this class ion super strong acid compound phase, and possesses particular performances, is expected to become a kind of material and catalyst that possesses unique effects.
Summary of the invention
The objective of the invention is in order to design the synthetic class organic ion super acids that the acidity suitable with super acids has ionic liquid character again that has.
Concrete technical scheme of the present invention is: the invention provides a kind of ion super strong acid, the structure of its architectural feature is:
Wherein
R is the high molecular polymer group, as polyethylene
(CF
2) among the n (n≤8)
Y is BF
4 -, PF
6 -, Tf
2N
-((CF
3SO
2)
2N
-), TA
-(CF
3COO
-), NO
3 -, EtSO
4 -Deng anion.
The present invention also provides the synthetic method of above-claimed cpd, and reaction equation of the present invention is as follows:
Solvent adds CaH again through the BaO drying and distilling before use
2Second distillation.Imidazoles and derivative thereof are in 80～110 ℃ of oven dry.Water is through distillation, deoxidation.At 0 ℃, under the inert gas shielding, in the over dry solvent suspension liquid of NaH, dropwise add the solution of imidazoles and derivative thereof.Above-mentioned reactant liquor adds catalyst after stirring 30～60min, stir 5～10min again after, add X (CF
2) nX reacts 2～3h, the cancellation of reactant liquor water, abstraction purification, MgSO between 25～60 ℃
4Drying gets product 1.In deoxidized water, add sodium acid carbonate, DMF, NaS under the inert gas shielding
2O
4And above-mentioned product 1, heating 60～80 ℃ of reaction 3～5h, evaporate to dryness reactant liquor solvent with isopropyl alcohol extraction, solvent evaporated, with benzene washing, vacuum drying, gets product 2.Product 2 is used hydrogen peroxide oxidation, gets product 3.Product 3 gets product 4 by acidic resins ion-exchange.
Product 4 mixes with acetonitrile and halo high molecular polymer, stirs 46～51h under 65～100 ℃ temperature, is cooled to the room temperature purifying after reaction is finished.Be dissolved in anhydrous methylene chloride again, under the ice-water bath condition, slowly drip the compound that produces the Y anionic group, and constantly stir.Dropwise the back and under 35～90 ℃ of conditions, add thermal agitation 45～54h, carry out decompression distillation after reaction is finished, promptly get ion super strong acid.
The specific embodiment
The invention will be further described below by example, but do not limit protection scope of the present invention.
Embodiment one:
1. at 0 ℃, under the inert gas shielding, in the over dry DMF of NaH suspension, dropwise add the DMF solution of imidazoles.Above-mentioned reactant liquor adds TBAI after stirring 55min, stir 5min again after, add Br (CF
2)
4Br reacts 2～3h (TLC detection), the cancellation of reactant liquor water, abstraction purification, MgSO between 25～30 ℃
4Drying gets product 1-(4-bromine octafluoro butyl) imidazoles, productive rate 66%.
2. in deoxidized water, add sodium acid carbonate, DMF, NaS under the inert gas shielding
2O
4And above-mentioned steps 1 products therefrom, heating 80 ℃ of reaction 3.5h, evaporate to dryness reactant liquor solvent with isopropyl alcohol extraction, solvent evaporated, with benzene washing, vacuum drying, gets product 4-imidazoles octafluoro for butyl sulfinic acid sodium, productive rate 82%.
3. above-mentioned steps 2 products therefroms are soluble in water, dropwise add 50% H
2O
2, stirring at room 2h, reaction finishes and steams water and excessive H
2O
2, use CH then respectively
2Cl
2, petroleum ether, product 4-imidazoles octafluoro for butyl sulfonic acid sodium, productive rate 84%
4. above-mentioned steps 3 products therefroms get product 4-imidazoles octafluoro for butyl sulfonic acid, productive rate 96% by acidic resins ion-exchange.
5. above-mentioned steps 4 products therefroms and bromo polyethylene mix with acetonitrile, stir 48h down at 95 ℃, are cooled to the room temperature purifying after reaction is finished.Be dissolved in anhydrous methylene chloride again, under the ice-water bath condition, slowly drip CF
3CF
2SO
3H, and constantly stir.Dropwise the back and under 70 ℃ of conditions, add thermal agitation 44h, carry out decompression distillation after reaction is finished, promptly get the product ion super acids, productive rate 81%.
Embodiment two:
1. at 0 ℃, under the inert gas shielding, at the over dry CH of NaH
3The CH that dropwise adds imidazoles in the CN suspension
3CN solution.Above-mentioned reactant liquor adds TBAI after stirring 60min, stir 10min again after, add Br (CF
2)
6Br is at 45 ℃ of reaction 3h (TLC detection), the cancellation of reactant liquor water, abstraction purification, MgSO
4Drying gets product 1-(6-bromine ten difluoro hexyls) imidazoles, productive rate 51%.
2. in deoxidized water, add sodium acid carbonate, DMF, NaS under the inert gas shielding
2O
4And above-mentioned steps 1 products therefrom, heating 80 ℃ of reaction 3.5h, evaporate to dryness reactant liquor solvent with isopropyl alcohol extraction, solvent evaporated, with benzene washing, vacuum drying, gets product 6-imidazoles 12 fluoro hexyl sulfinic acid sodium, productive rate 81%.
3. above-mentioned steps 2 products therefroms are soluble in water, dropwise add 50% H
2O
2, stirring at room 4h, reaction finishes and steams water and excessive H
2O
2, use CH then respectively
2Cl
2, petroleum ether, product 6-imidazoles 12 fluoro hexyl sodium sulfonates, productive rate 86%
4. above-mentioned steps 3 products therefroms get product 6-imidazoles 12 fluoro hexyl sulfonic acid, productive rate 93% by acidic resins ion-exchange.
5. above-mentioned steps 4 products therefroms and chlorinated polyethylene mix with acetonitrile, stir 50h down at 95 ℃, are cooled to the room temperature purifying after reaction is finished.Be dissolved in anhydrous methylene chloride again, under the ice-water bath condition, slowly drip hexafluorophosphoric acid, and constantly stir.Dropwise the back and under 80 ℃ of conditions, add thermal agitation 47h, carry out decompression distillation after reaction is finished, promptly get the product ion super acids, productive rate 79%.
Claims (9)
1, ion super strong acid compound is characterized in that the structure of this compound is:
Wherein
R is the high molecular polymer group, as polyvinyl;
n＝1～8；
Y is BF
4 -, PF
6 -, Tf
2N
-((CF
3SO
2)
2N
-), TA
-(CF
3COO
-), NO
3 -, EtSO
4 -Deng anion.
2, according to claim 1 described ion super strong acid, it is characterized in that, contain group-CF
2SO
3H.
3, according to claim 1 described ion super strong acid, it is characterized in that, contain the group imidazole cation group.
4, according to claim 1 described ion super strong acid, it is characterized in that pbz polymer material group.
5, according to claim 1 described ion super strong acid preparation method, it is characterized in that
(1) solvent adds CaH again through the BaO drying and distilling before use
2Second distillation.Imidazoles and derivative thereof are in 80～110 ℃ of oven dry.Water is through distillation, deoxidation.
(2), under the inert gas shielding, in the over dry solvent suspension liquid of NaH, dropwise add the solution of imidazoles and derivative thereof at 0 ℃.Above-mentioned reactant liquor adds catalyst after stirring 30～60min, stir 5～10min again after, add X (CF
2) nX reacts 2～3h, the cancellation of reactant liquor water, abstraction purification, MgSO between 25～60 ℃
4Drying gets product 1.
(3) in deoxidized water, add sodium acid carbonate, DMF, NaS under the inert gas shielding
2O
4And above-mentioned product 1, heating 60～80 ℃ of reaction 3～5h, evaporate to dryness reactant liquor solvent with isopropyl alcohol extraction, solvent evaporated, with benzene washing, vacuum drying, gets product 2.
(4) product 2 is used hydrogen peroxide oxidation, gets product 3.
(5) product 3 gets product 4 by acidic resins ion-exchange.
(6) product 4 mixes with acetonitrile and halo high molecular polymer, stirs 46～51h 65～100 ℃ temperature, is cooled to the room temperature purifying after reaction is finished.Be dissolved in anhydrous methylene chloride again, under the ice-water bath condition, slowly drip the compound that produces the Y anionic group, and constantly stir.Dropwise the back and under 35～90 ℃ of conditions, add thermal agitation 45～54h, carry out decompression distillation after reaction is finished, promptly get ion super strong acid.
6, described according to claim 5
(1) imidazoles and derivative thereof: imidazoles, benzimidazole, 2-tolimidazole, 5,6-dimethylbenzimidazole.
(2) solvent is DMF or CH
3CN.
(3) X (CF
2) nX, (n≤8, X is Cl, Br, I).
7,, it is characterized in that described inert gas is nitrogen, helium according to claim 5 described preparation methods.
8,, it is characterized in that catalyst is Bu according to claim 5 (1) described preparation methods
4NI.
9, according to claim 5 described preparation methods, the solvent place selected the DMF effect than CH when reactant was NaH
3CN is better.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102337014A CN101422744A (en) | 2008-12-10 | 2008-12-10 | Ion super strong acid and synthesis method thereof |
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|---|---|---|---|
| CNA2008102337014A CN101422744A (en) | 2008-12-10 | 2008-12-10 | Ion super strong acid and synthesis method thereof |
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|---|---|
| CN101422744A true CN101422744A (en) | 2009-05-06 |
Family
ID=40613761
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|---|---|---|---|
| CNA2008102337014A Pending CN101422744A (en) | 2008-12-10 | 2008-12-10 | Ion super strong acid and synthesis method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815690A (en) * | 2015-04-14 | 2015-08-05 | 贵州大学 | Multi-sulfonic acid funtionalized mesoporous polymeric solid acid catalyst and preparation method and application thereof |
| CN106811135A (en) * | 2017-01-11 | 2017-06-09 | 中国工程物理研究院机械制造工艺研究所 | A kind of oily bag acidic ion liquid polishing fluid for KDP crystal |
-
2008
- 2008-12-10 CN CNA2008102337014A patent/CN101422744A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104815690A (en) * | 2015-04-14 | 2015-08-05 | 贵州大学 | Multi-sulfonic acid funtionalized mesoporous polymeric solid acid catalyst and preparation method and application thereof |
| CN106811135A (en) * | 2017-01-11 | 2017-06-09 | 中国工程物理研究院机械制造工艺研究所 | A kind of oily bag acidic ion liquid polishing fluid for KDP crystal |
| CN106811135B (en) * | 2017-01-11 | 2018-07-06 | 中国工程物理研究院机械制造工艺研究所 | A kind of oily packet acidic ion liquid polishing fluid for KDP crystal |
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| PB01 | Publication | ||
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Application publication date: 20090506 |