CN1580029A - (Methyl) acrylic acid series ion liquid and its preparing method - Google Patents
(Methyl) acrylic acid series ion liquid and its preparing method Download PDFInfo
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- CN1580029A CN1580029A CN 03153349 CN03153349A CN1580029A CN 1580029 A CN1580029 A CN 1580029A CN 03153349 CN03153349 CN 03153349 CN 03153349 A CN03153349 A CN 03153349A CN 1580029 A CN1580029 A CN 1580029A
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- ionic liquid
- methyl
- methylimidazole
- acrylic type
- liquid
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Abstract
The invention refers to a kind of (methyl) acrylic hydronium liquid and its preparation method. The new hydronium liquid in the invention is the monomer used to produce new polyelectrolyte, also can be copolymerized with other monomers to produce corresponding new high molecular material and belongs to the field of new green chemical material and preparation technology. The acrylic hydronium liquid is produced by means of the double decomposition reaction among the (methyl) crylic acid, silver oxide and positive ion compound. The invention is featured by the simple preparation method and low cost and can be applied to the mass production.
Description
Technical field
The present invention relates to class ionic liquid and preparation method thereof, especially a class is novel contains (methyl) acrylic type ionic liquid of polymerizable double bond and preparation method thereof.This class novel ion liquid is the polymerization single polymerization monomer of the novel polyelectrolyte of preparation, also can prepare corresponding novel high polymer material with existing other monomer copolymerization, belongs to novel green chemical material and preparing technical field thereof.
Background technology
Ionic liquid at room temperature is the liquid of being made up of positively charged ion and negatively charged ion fully, and it is in a liquid state under＜100 ℃, and viscosity is lower, therefore is called watery fusion salt again.Ionic liquid at room temperature self has some distinguishing features, and more shallow as color, nothing is smelt; Almost there is not vapour pressure, non-volatile; Bigger equilibrium temperature scope; Nonflammable explosive; Better chemical stability; The electrochemical stability current potential form of broad; Can adjust its solvability and acidity or the like by the design of zwitterion, therefore promptly can be used as excellent green reaction medium, have catalysis again, be widely used in electrochemistry, catalysis, separation, chemistry and biochemical reaction etc. material.At present, the general ionic liquid of Shi Yonging, the positively charged ion during it is formed mainly contains quaternary ammonium alkyl positively charged ion, Wan Ji quaternary phosphine positively charged ion, 1, types such as 3-dialkylimidazolium positively charged ion (or being referred to as N, N '-dialkylimidazolium positively charged ion) and N-alkyl pyridine positively charged ion; Negatively charged ion mostly is BF
4 -, PF
6 -, [CF is also arranged
3SO
3]
-, AsF
6 -, (CF
3SO
2)
2N
-, CF
3COO
-, (CF
3SO
2)
3C
-, [SbF
6]
-Deng.And a class contains polymerizable double bond in structure special ion liquid just appearred first up to 2000, be N-vinyl imidazole tetrafluoroborate ion liquid (M Hirao, K Ito and H Ohno.Electrochimica Acta, 2000,45:1291), the cationic moiety of its structure has been introduced vinyl.At present, in article or patent, there is this class ionic liquid of report to comprise: diacetone acrylic amide type ionic liquid (Dan Yongkui, Dai Liyi, Cai Qinghai, He Mingyuan. the vinylsulfonate of Chinese patent application number 02111969.4 (publication number: CN1385243A)) and N-vinyl imidazole and 3 acrylic acid n-propyl sulfonate (the M Yoshizawa of N-vinyl imidazole, W Ogihara and H Ohno.Polymerfor Advanced Technologies 2002,13:589).Yet, in the prior art document (methyl) acrylic type ionic liquid involved in the present invention still is not reported up to now.
Summary of the invention
The purpose of this invention is to provide novel (methyl) acrylic type ionic liquid of a class.
Another object of the present invention provides this class preparation method of ionic liquid.
Therefore, one aspect of the present invention provides the ionic liquid of (methyl) acrylic type shown in the following general formula of a class (I):
M
+CH
2＝C(R′)COO
- (I)
M wherein
+And R ' such as hereinafter definition.
The present invention provides the ion liquid method of (methyl) acrylic type of a kind of above-mentioned general formula of preparation (I) on the other hand, this method comprises and adds silver suboxide, water and (methyl) vinylformic acid in the reactor successively, filter as required after the stirring at room reaction, under stirring at room, the aqueous solution of cationic source compound is added drop-wise in gained solution or the filtrate then, behind the reaction certain hour, obtain target product (methyl) acrylic type ionic liquid through separating treatment.
Detailed Description Of The Invention
The present invention relates to (methyl) acrylic type ionic liquid shown in the following general formula (I):
M
+CH
2＝C(R′)COO
- (I)
M wherein
+Be to be selected from following positively charged ion:
[NR
xH
4-x]
+, [PR
xH
4-x]
+,
Or
Wherein x is the integer of 1-4, R and R
1Mutually identical or different and represent C respectively
1-C
18Alkyl or C
7-13Aralkyl; With
R ' is H or CH
3
In the present invention, C
1-C
18The example of alkyl has methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group and isomer thereof, hexyl and isomer thereof, heptyl and isomer thereof, octyl group and isomer thereof, nonyl and isomer thereof, decyl and isomer thereof, undecyl and isomer thereof, dodecyl and isomer thereof, tridecyl and isomer thereof, tetradecyl and isomer thereof, pentadecyl and isomer thereof, hexadecyl and isomer thereof, heptadecyl and isomer thereof and octadecyl and isomer thereof; Preferred C
1-C
8Alkyl is as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, hexyl and isomer thereof, octyl group and isomer thereof; More preferably C
1-C
4Alkyl is as methyl, ethyl, normal-butyl, isobutyl-, sec-butyl or the tertiary butyl.
In the present invention, C
7-13The example of aralkyl has benzyl, styroyl, hydrocinnamyl or diphenyl methyl etc., preferred benzyl, styroyl etc.
In (methyl) acrylic type ionic liquid shown in the above-mentioned general formula (I), M
+Be preferably positively charged ion shown in the following formula:
Wherein R and R
1As defined above, preferred R represents C
1-C
18Alkyl or C
7-13Aralkyl, and R
1Represent C
1-C
18Alkyl; More preferably R represents normal-butyl or ethyl or benzyl, and R
1Represent methylidene.
The most preferred ionic liquid of the present invention is the acrylate ionic liquid of 1-normal-butyl-3-Methylimidazole, the methacrylate ionic liquid of 1-normal-butyl-3-Methylimidazole, the acrylate ionic liquid of 1-ethyl-3-Methylimidazole, the methacrylate ionic liquid of 1-ethyl-3-Methylimidazole, the acrylate ionic liquid of 1-benzyl-3-Methylimidazole, the methacrylate ionic liquid of 1-benzyl-3-Methylimidazole.
In the methods of the invention, used cationic source compound is corresponding to described cationic compound, and the example comprises halogenide such as muriate, bromide or iodide etc.
The first step of the inventive method relates to silver suboxide, water and (methyl) vinylformic acid is added in the reactor successively, and reacts under stirring at room.It is vinylformic acid or methacrylic acid that the length in reaction times depends on raw materials used, for example can for several minutes to several hours, be preferably 5 minutes to 5 hours, more preferably 10 minutes to 3 hours, most preferably be 20 minutes to 2 hours.
Filtration step in the inventive method is not essential, and this depends on that raw materials used is vinylformic acid or methacrylic acid.For example when using vinylformic acid, filtration step must be carried out, and when using methacrylic acid, filtration step needn't be carried out usually.
After the reaction of (methyl) vinylformic acid and silver suboxide is finished and after optional filtration step, the aqueous solution with the cationic source compound directly is added drop-wise in gained solution or the filtrate usually, reacts in room temperature with under stirring then.Described reaction can be finished after the aqueous solution of cationic source compound drips soon with the direct precipitation mode of by product.The cationic source compound is 1: 1 with (methyl) acrylic acid mol ratio.
After finishing, described by product precipitation obtains target (methyl) acrylic type ionic liquid through separating to handle.Without any particular determination, for example can use conventional filtration, centrifugation and distillation to the employing separate mode.
Novel (methyl) of the present invention acrylic type ionic liquid and preparation method thereof compared with prior art has following distinguishing feature:
(1) the present invention is to provide a class novel ion liquid, developed ion liquid new variety.
(2) under thought guidance of the present invention, can obtain the ionic liquid of multiple different structure and character according to concrete needs.
(3) ionic liquid of the present invention not only has ion liquid in the past function, especially can synthesize new polyelectrolyte as the monomer of polyreaction.This ionogen will be because the existence of ionic liquid structure will have excellent specific function.In addition, ionic liquid of the present invention also can prepare corresponding novel high polymer material with existing other monomer copolymerization.
(4) the related reaction of this synthetic method is replacement(metathesis)reaction, and simple to operate, required equipment is few, is easy to obtain purer product, and cost is lower, is suitable for large-scale commercial production.
Embodiment
The acrylate ionic liquid of embodiment 1:1-normal-butyl-3-Methylimidazole
Take by weighing 2.32g (about 0.02mol) silver suboxide,, add 1.44g (0.02mol) vinylformic acid again 200ml deionized water for stirring 10 minutes, after stirring at room is reacted about 2 hours, the filtering reaction thing.The 20ml aqueous solution (about 20wt%) that will contain 4.38g (0.02mol) BmimBr (bromination 1-butyl-3-methylimidazole salt, its preparation method referring to Chinese patent application 02130963.9, reference example 1) is added drop-wise in the filtrate does not separate out to there being the oyster precipitation.Leach the oyster precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
The methacrylate ionic liquid of embodiment 2:1-normal-butyl-3-Methylimidazole
Take by weighing 2.32g (about 0.02mol) silver suboxide, 200ml deionized water for stirring 10 minutes, add 1.72g (0.02mol) methacrylic acid again, stirring at room is reacted did not have insolubles in about 10 minutes to system.The 20ml aqueous solution (about 20wt%) that will contain 4.38g (0.02mol) BmimBr (with embodiment 1) is added drop-wise in the filtrate does not separate out to there being the oyster precipitation.Leach the oyster precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.
The acrylate ionic liquid of embodiment 3:1-ethyl-3-Methylimidazole
Take by weighing 2.32g (about 0.02mol) silver suboxide,, add 1.44g (0.02mol) vinylformic acid again 200ml deionized water for stirring 10 minutes, after stirring at room is reacted about 2 hours, the filtering reaction thing.The 20ml aqueous solution (about 20wt%) that will contain 3.82g (0.02mol) EmimBr (bromination 1-ethyl-3-methylimidazole salt, its preparation method referring to Chinese patent application 03121575.0, reference example 1) is added drop-wise in the filtrate does not separate out to there being the oyster precipitation.Leach the oyster precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
The methacrylate ionic liquid of embodiment 4:1-ethyl-3-Methylimidazole
Take by weighing 2.32g (about 0.02mol) silver suboxide, stirred 10 minutes in 200ml water, add 1.72g (0.02mol) methacrylic acid again, stirring at room is reacted did not have insolubles in about 10 minutes to system.The 20ml aqueous solution (about 20wt%) that will contain 3.82g (0.02mol) EmimBr (with embodiment 3) is added drop-wise in the filtrate does not separate out to there being the oyster precipitation.Leach the oyster precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
The acrylate ionic liquid of embodiment 5:1-normal-butyl-3-Methylimidazole (method two, method see embodiment 1)
Take by weighing 2.32g (about 0.02mol) silver suboxide,, add 1.44g (0.02mol) vinylformic acid again 200ml deionized water for stirring 10 minutes, after stirring at room is reacted about 2 hours, the elimination insolubles.The 20ml aqueous solution (about 20wt%) that will contain 3.49g (0.02mol) BmimCl (chlorination 1-butyl-3-methylimidazole salt, its preparation method see reference embodiment 1) is added drop-wise in the filtrate does not separate out to there being light gray purple precipitation.Leach light gray purple precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
The methacrylate ionic liquid of embodiment 6:1-normal-butyl-3-Methylimidazole (method two, method see embodiment 2)
Take by weighing 2.32g (about 0.02mol) silver suboxide, 200ml deionized water for stirring 10 minutes, add 1.72g (0.02mol) methacrylic acid again, stirring at room is reacted did not have insolubles in about 10 minutes to system.The aqueous solution 20ml (about 20wt%) that will contain 3.49g (0.02mol) BmimCl (with embodiment 5) is added drop-wise in the filtrate and does not separate out to there being light gray purple precipitation.Leach light gray purple precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
The acrylate ionic liquid of embodiment 7:1-benzyl-3-Methylimidazole
Take by weighing 2.32g (about 0.02mol) silver suboxide,, add 1.44g (0.02mol) vinylformic acid again 200ml deionized water for stirring 10 minutes, after stirring at room is reacted about 2 hours, the elimination insolubles.The 20ml aqueous solution (about 20wt%) that will contain 4.17g (0.02mol) chlorination 1-benzyl-3-methylimidazole salt (its preparation method see reference embodiment 2) is added drop-wise in the filtrate does not separate out to there being light gray purple precipitation.Leach light gray purple precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
The methacrylate ionic liquid of embodiment 8:1-benzyl-3-Methylimidazole
Take by weighing 2.32g (about 0.02mol) silver suboxide, 200ml deionized water for stirring 10 minutes, add 1.72g (0.02mol) methacrylic acid again, stirring at room is reacted did not have insolubles in about 10 minutes to system.The 20ml aqueous solution (about 20wt%) that will contain 4.17g (0.02mol) chlorination 1-benzyl-3-methylimidazole salt (with embodiment 7) is added drop-wise in the filtrate does not separate out to there being light gray purple precipitation.Leach light gray purple precipitation, dewater, obtain corresponding ionic liquid through revolving to steam.Productive rate is greater than 95%.Reaction formula is:
Reference example 1: the preparation of chlorination 1-butyl-3-methylimidazole salt
Measure 20ml (0.250mol) 1-Methylimidazole respectively and 28.5ml (0.272mol) 1-chlorobutane joins in the 250ml there-necked flask, magnetic agitation, reflux 12 hours obtains glassy yellow clear liquid, productive rate 89.7%.
Reference example 2: the preparation of chlorination 1-benzyl-3-methylimidazole salt
Measure 5ml (0.063mol) 1-Methylimidazole respectively and 8.0ml (0.070mol) benzyl chloride joins in the 100ml single port flask, stirring at room 2 hours obtains colourless viscous liquid, and productive rate is greater than 96%.
Claims (8)
1. (methyl) acrylic type ionic liquid shown in the following general formula (I):
M
+CH
2＝C(R′)COO
- (I)
M wherein
+Be to be selected from following positively charged ion:
[NR
xH
4-x]
+, [PR
xH
4-x]
+,
Or
Wherein x is the integer of 1-4, R and R
1Mutually identical or different and represent C respectively
1-C
18Alkyl or C
7-13Aralkyl; With
R ' is H or CH
3
2. according to (methyl) acrylic type ionic liquid of claim 1, M wherein
+Be positively charged ion shown in the following formula:
Wherein R and R
1Such as claim 1 definition.
3. according to (methyl) acrylic type ionic liquid of claim 2, wherein R represents C
1-C
18Alkyl or C
7-13Aralkyl, and R
1Represent C
1-C
18Alkyl.
4. according to (methyl) acrylic type ionic liquid of claim 3, wherein R represents normal-butyl, ethyl or benzyl, and R
1Represent methylidene.
5. according to each (methyl) acrylic type ionic liquid among the claim 1-4, it is the acrylate ionic liquid of 1-normal-butyl-3-Methylimidazole, the methacrylate ionic liquid of 1-normal-butyl-3-Methylimidazole, the acrylate ionic liquid of 1-ethyl-3-Methylimidazole, the methacrylate ionic liquid of 1-ethyl-3-Methylimidazole, the acrylate ionic liquid of 1-benzyl-3-Methylimidazole, the methacrylate ionic liquid of 1-benzyl-3-Methylimidazole.
6. ion liquid method of (methyl) acrylic type for preparing the described general formula of claim 1 (I), this method comprises and adds silver suboxide, water and (methyl) vinylformic acid in the reactor successively, filter as required after the stirring at room reaction, under stirring at room, the aqueous solution of cationic source compound is added drop-wise in gained solution or the filtrate then, obtains required (methyl) acrylic type ionic liquid through separating to handle after reaction for some time.
7. according to the method for claim 6, wherein the cationic source compound is 1: 1 with (methyl) acrylic acid mol ratio.
8. according to the method for claim 6 or 7, wherein said cationic source compound is the defined cationic halogenide of claim 1 such as muriate, bromide or iodide etc.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153349 CN1255372C (en) | 2003-08-11 | 2003-08-11 | (Methyl) acrylic acid series ion liquid and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03153349 CN1255372C (en) | 2003-08-11 | 2003-08-11 | (Methyl) acrylic acid series ion liquid and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1580029A true CN1580029A (en) | 2005-02-16 |
| CN1255372C CN1255372C (en) | 2006-05-10 |
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355737C (en) * | 2006-03-22 | 2007-12-19 | 华东师范大学 | Pyruvic acid type ionic liquid and its preparing method |
| DE102008002927A1 (en) | 2007-07-19 | 2009-01-08 | Basf Se | Mixtures containing free radical polymerization inhibitors and ionic liquids, and their use for stabilizing radically polymerizable monomers |
| CN102906133A (en) * | 2010-05-18 | 2013-01-30 | 3M创新有限公司 | Polymerizable ionic liquid compositions |
| CN101993418B (en) * | 2009-08-21 | 2013-08-07 | 北京师范大学 | (Methyl) acrylamido carboxylate ionic liquid and preparation method thereof |
| CN108102022A (en) * | 2017-11-20 | 2018-06-01 | 南通诺为新材料科技有限公司 | A kind of polypropylene flame redardant acids plastics and preparation method and application |
-
2003
- 2003-08-11 CN CN 03153349 patent/CN1255372C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100355737C (en) * | 2006-03-22 | 2007-12-19 | 华东师范大学 | Pyruvic acid type ionic liquid and its preparing method |
| DE102008002927A1 (en) | 2007-07-19 | 2009-01-08 | Basf Se | Mixtures containing free radical polymerization inhibitors and ionic liquids, and their use for stabilizing radically polymerizable monomers |
| CN101993418B (en) * | 2009-08-21 | 2013-08-07 | 北京师范大学 | (Methyl) acrylamido carboxylate ionic liquid and preparation method thereof |
| CN102906133A (en) * | 2010-05-18 | 2013-01-30 | 3M创新有限公司 | Polymerizable ionic liquid compositions |
| CN102906133B (en) * | 2010-05-18 | 2015-11-25 | 3M创新有限公司 | Polymerisable ionic liquid compositions |
| CN108102022A (en) * | 2017-11-20 | 2018-06-01 | 南通诺为新材料科技有限公司 | A kind of polypropylene flame redardant acids plastics and preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1255372C (en) | 2006-05-10 |
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Granted publication date: 20060510 Termination date: 20100811 |