CN102229530B - Clean production method for perfluoroalkyl acrylate - Google Patents
Clean production method for perfluoroalkyl acrylate Download PDFInfo
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- CN102229530B CN102229530B CN2011101223997A CN201110122399A CN102229530B CN 102229530 B CN102229530 B CN 102229530B CN 2011101223997 A CN2011101223997 A CN 2011101223997A CN 201110122399 A CN201110122399 A CN 201110122399A CN 102229530 B CN102229530 B CN 102229530B
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- fluorine
- reaction
- negative pressure
- alcohol
- vinylformic acid
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Abstract
The invention relates to a clean production method for perfluoroalkyl acrylate, which belongs to the field of preparation of intermediates containing fluorine. The technical scheme for the method is as follows: in a reaction vessel with a negative pressure water separator, under the condition of a negative pressure of -0.04 to -0.085 Mpa and a temperature of 110 to 120 DEG C, under the action of an alkali metal acid salt catalyst and a polymerization inhibitor, perfluoro alcohol reacts with acrylic acid or homologues thereof to generate perfluoroalkyl acrylate, wherein perfluoro alcohol refers to fluorine-containing alcohol which has a general formula of F(CF2CF2)n(CH2)mOH, n therein is a positive integer from 1 to 10, m therein is 1 or 2 or 3, and alkali metal acid salt is potassium bisulfate or sodium bisulfate. According to the invention, the negative pressure water separator is used to separate resultant moisture in time, which enables a more adequate reaction and a high conversion rate of acrylic acid; no azeotropic organic solvent is used and water generated in the reaction can be recycled directly; after the reaction ends, the catalyst precipitates with the decrease of temperature and can be removed by merely filtering, thereby achieving the purpose of clean production.
Description
Technical field
The present invention relates to a kind of fluoro-containing intermediate preparation field, the method for the fluorine-containing alkyl acrylate of particularly a kind of cleaner production.
Background technology
Perfluoroalkyl acrylate is the key intermediate of synthetic fluorine-containing textile finishing agent.Bibliographical information, under the Catalyzed by p-Toluenesulfonic Acid effect, the water that utilizes benzene, toluene and reaction to produce forms the azeotropic body; Thereby take water out of, make more abundant that reaction can carry out, the patent documentation of this respect has a lot; Just do not enumerated, still, in the last handling process of this reaction; Need water to come flush away catalyst for reaction---tosic acid, produce great amount of wastewater, and after benzene, toluene and water azeotropic slip out; Also need further separate and to discharge or recycle, increase the cost of postprocessing working procedures.
Also have method through transesterify to prepare perfluoroalkyl acrylate; But in aftertreatment, also need water to clean and remove another one alcohol; Thereby generation great amount of wastewater, people expectation have kind of economy simple and can make reaction process reach the preparation method of zero release.
Summary of the invention
Prepare in the process problem that produces great amount of wastewater in order to solve above perfluoroalkyl acrylate, it is simple and can make reaction process reach method zero release, that can not produce the fluorine-containing alkyl acrylate of cleaner production of great amount of wastewater in the last handling process to the invention provides a kind of economy.
The present invention realizes through following measure:
The method of the fluorine-containing alkyl acrylate of a kind of cleaner production; Be in the reaction vessel that has the negative pressure water trap; Negative pressure-0.04～-0.085Mpa; Under 110～120 ℃ of the temperature, under basic metal hydrogen salt catalyzer and stopper effect, fluorine-containing alcohol and vinylformic acid or the reaction of its homologue generate fluorine-containing alkyl acrylate;
Said fluorine-containing alcohol is meant that general formula is F (CF
2CF
2)
n(CH
2)
mThe fluorine-containing alcohol of OH, wherein: n is the positive integer of 1-10, m=1,2 or 3.
Said basic metal hydrogen salt is sal enixum or sodium pyrosulfate.
Said vinylformic acid or its homologue have general formula CH
2=CXCOOH, X=H, CH
3
Preferred n is 3 or 4, preferred m=2.
Said fluorine alcohol is 1:0.01～0.03 with the weight ratio of basic metal hydrogen salt.
Fluorine alcohol is 1:0.5～1 with the mol ratio of vinylformic acid or its homologue.
Preferred fluorine alcohol is 1:0.8 with the mol ratio of vinylformic acid or its homologue.
Negative pressure water trap top temperature >=60 ℃.
Preferred stopper is Resorcinol and 4-methoxyl group phenol.
The catalyzer, the fluorine-containing alcohol that reclaim can recycle.
Beneficial effect of the present invention:
(1) entire reaction is carried out under negative pressure, utilizes the negative pressure water trap that the moisture that produces is in time separated, and makes reaction more abundant; The vinylformic acid transformation efficiency is high, and method is easy, and reaction can steadily be carried out; Do not use the azeotropic organic solvent; The water that produces can directly be recycled, and need not to separate, and reaches the purpose of cleaner production;
(2) after reaction finished, along with the reduction of temperature, catalyzer was separated out, and just can remove through simple filtering, need not use big water gaging to clean, thereby reaches the purpose of cleaner production.
Embodiment
Following examples help to understand the present invention, but are not limited to following content:
Embodiment 1
On 1L four-hole vial, configuration negative pressure water trap, whisking appliance, TM, prolong.Add perfluoro hexyl ethanol 728 g (2mol) successively, vinylformic acid 115g (1.6 mol), catalyst sulfuric acid hydrogen potassium 7.3g.Hydroquinone of polymerization retarder 1.2g, 4-methoxyl group phenol 0.5g.Stir and heat temperature raising, a temperature is 110～120 ℃ in the control bottle, pressure is-0.04～-0.08Mpa; React; Control water trap top temperature >=60 ℃, the water band that utilizes water trap will react generation in the reaction process leaves reactant, and the raw material fluorine alcohol of taking out of is put back in the bottle again.No longer include water generates after 8 hours, stopped reaction.Moisture 28g is taken in metering out of.Reaction solution is cooled to room temperature, and catalyzer is separated out, and removes by filter catalyzer, obtains perfluor alkyl ethide propenoate bullion, and each component content sees the following form 1.Behind the rectifying purifying, obtain perfluoro hexyl ethyl propylene acid esters product.
Table 1 reaction product composition analysis result
| Title | Content (%) |
| Perfluoro hexyl ethanol | 17.64 |
| Vinylformic acid | 0.12 |
| Perfluoro hexyl ethyl propylene acid esters | 78.45 |
Calculate vinylformic acid transformation efficiency 99.15%.
Embodiment 2
Adjustment reactant perfluoro hexyl ethanol and acrylic acid mol ratio are 1:1, and the weight ratio of perfluoro hexyl ethanol and catalyzer is 1:0.01, reacts, and technology is identical with embodiment 1, and moisture 31.5g is taken in metering out of.Each component content is seen table 2 in the perfluoro hexyl ethyl propylene acid esters bullion
Table 2 reaction product composition analysis result
| Title | Content (%) |
| Perfluoro hexyl ethanol | 8.50 |
| Vinylformic acid | 1.55 |
| Perfluoro hexyl ethyl propylene acid esters | 87.6 |
Calculate vinylformic acid transformation efficiency 90.96%.
Embodiment 3
Adjustment reactant perfluoro hexyl ethanol and acrylic acid mol ratio are 1:0.8, and the weight ratio of perfluoro hexyl ethanol and catalyzer is 1:0.03, reacts, and technology is identical with embodiment 1.Each component content is seen table 3 in the perfluoro hexyl ethyl propylene acid esters bullion.
Table 3 reaction product composition analysis result
| Title | Content (%) |
| Perfluoro hexyl ethanol | 17.21 |
| Vinylformic acid | 0.15 |
| Perfluoro hexyl ethyl propylene acid esters | 79.51 |
Calculate vinylformic acid transformation efficiency 98.94%.
Embodiment 4
Adjustment reactant perfluoro octyl ethanol and acrylic acid mol ratio are 1:0.8, and the weight ratio of perfluoro octyl ethanol and catalyzer is 1:0.03, reacts, and technology is identical with embodiment 1.Each component content is seen table 4 in the perfluoro capryl ethyl propylene acid esters bullion.
Table 4 reaction product composition analysis result
| Title | Content (%) |
| Perfluoro octyl ethanol | 18.32 |
| Vinylformic acid | 0.07 |
| Perfluoro capryl ethyl propylene acid esters | 79.54 |
Calculate vinylformic acid transformation efficiency 99.38%.
Embodiment 5
On 1L four-hole vial, configuration negative pressure water trap, whisking appliance, TM, prolong.Add perfluoro octyl ethanol 928g (2mol) successively, methylacrylic acid 138g (1.6mol), catalyst sulfuric acid hydrogen sodium 18.5g, hydroquinone of polymerization retarder 1.5g, 4-methoxyl group phenol 0.75g.Stirring and heat temperature raising, make bottle interior temperature at 110～120 ℃, pressure is-0.06～-0.085MPa; React; Control water trap top temperature >=60 ℃, the water band that utilizes water trap will react generation in the reaction process leaves reactant, and the raw material fluorine alcohol of taking out of is put back in the bottle again.No longer include water generates after 5 hours, stopped reaction, moisture 29.5g is taken in metering out of.Reaction solution is cooled to room temperature, and catalyzer is separated out, and filters, and removes catalyzer, obtains perfluoro capryl ethyl propylene acid esters bullion, and each component content is seen table 5.Behind the purifying, obtain perfluoro capryl ethyl propylene acid esters product.
Table 5 reaction product composition analysis result
| Title | Content (%) |
| Perfluoro octyl ethanol | 17.64 |
| Vinylformic acid | 0.1 |
| Perfluoro capryl ethyl propylene acid esters | 77.95 |
Calculate methylacrylic acid transformation efficiency 99.25%.
Embodiment 6
The mol ratio of perfluoro hexyl ethanol and perfluoro octyl ethanol is 1:1; Total mole number and acrylic acid mol ratio are 1:0.85; The gross weight of perfluoro hexyl ethanol and perfluoro octyl ethanol and the weight ratio of catalyzer are 1:0.015, react, and technology is identical with embodiment 5.Each component content is seen table 6 in the gained bullion.
Table 6 reaction product composition analysis result
| Title | Content (%) |
| Perfluoro hexyl ethanol | 5.96 |
| Perfluoro octyl ethanol | 10.1 |
| Vinylformic acid | 0.16 |
| The perfluor alkyl ethide propenoate | 78.2 |
Calculate vinylformic acid transformation efficiency 98.73%.
The fluorine alcohol that reclaims when catalyzer that use is reclaimed and purifying reacts, and also can reach effect same, no longer one by one statement.
Claims (7)
1. the method for the fluorine-containing alkyl acrylate of cleaner production; It is characterized in that in the reaction vessel that has the negative pressure water trap; Negative pressure-0.04～-0.085Mpa; Under 110～120 ℃ of the temperature, under basic metal hydrogen salt catalyzer and stopper effect, fluorine-containing alcohol and vinylformic acid or the reaction of its homologue generate fluorine-containing alkyl acrylate;
Said fluorine-containing alcohol is meant that general formula is F (CF
2CF
2)
n(CH
2)
mThe fluorine alcohol of OH, wherein: n is the positive integer of 1-10, m=1,2 or 3;
Said basic metal hydrogen salt is sal enixum or sodium pyrosulfate;
Said vinylformic acid or its homologue have general formula CH
2=CXCOOH, X=H, CH
3
2. method according to claim 1 is characterized in that n is 3 or 4, m=2.
3. method according to claim 1 is characterized in that the said fluorine alcohol and the weight ratio of basic metal hydrogen salt are 1:0.01～0.03.
4. method according to claim 1 is characterized in that the fluorine alcohol and the mol ratio of vinylformic acid or its homologue are 1:0.5～1.
5. method according to claim 1 is characterized in that the fluorine alcohol and the mol ratio of vinylformic acid or its homologue are 1:0.8.
6. method according to claim 1 is characterized in that negative pressure water trap top temperature >=60 ℃.
7. method according to claim 1 is characterized in that stopper is Resorcinol and 4-methoxyl group phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101223997A CN102229530B (en) | 2011-05-12 | 2011-05-12 | Clean production method for perfluoroalkyl acrylate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101223997A CN102229530B (en) | 2011-05-12 | 2011-05-12 | Clean production method for perfluoroalkyl acrylate |
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|---|---|
| CN102229530A CN102229530A (en) | 2011-11-02 |
| CN102229530B true CN102229530B (en) | 2012-06-06 |
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| CN2011101223997A Expired - Fee Related CN102229530B (en) | 2011-05-12 | 2011-05-12 | Clean production method for perfluoroalkyl acrylate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766049A (en) * | 2012-07-24 | 2012-11-07 | 上海和创化学科技有限公司 | Preparation method of ethyl methacrylate |
| CN105085868A (en) * | 2015-09-25 | 2015-11-25 | 南通星辰合成材料有限公司 | Method for synthesizing phenolic ketone epoxy resin through negative pressure water separation |
| CN109867599A (en) * | 2019-02-28 | 2019-06-11 | 西南交通大学 | A kind of big steric hindrance structure perfluor big molecular modification agent and preparation method |
| CN114292191A (en) * | 2021-12-17 | 2022-04-08 | 重庆新氟科技有限公司 | Preparation method of fluorine-containing methacrylic acid monomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400633A (en) * | 2006-03-10 | 2009-04-01 | 优迈特株式会社 | Polyfluoroalkyl alcohol or (meth)acrylic acid derivative thereof, and their production methods |
| CN101765614A (en) * | 2007-07-25 | 2010-06-30 | 纳幕尔杜邦公司 | fluoropolymer emulsions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3852249B2 (en) * | 1998-07-31 | 2006-11-29 | 旭硝子株式会社 | Fluorine-containing compound, production method thereof, fluorine-containing polymer, and use thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101400633A (en) * | 2006-03-10 | 2009-04-01 | 优迈特株式会社 | Polyfluoroalkyl alcohol or (meth)acrylic acid derivative thereof, and their production methods |
| CN101765614A (en) * | 2007-07-25 | 2010-06-30 | 纳幕尔杜邦公司 | fluoropolymer emulsions |
Non-Patent Citations (1)
| Title |
|---|
| 周钰明 等."对甲苯磺酸催化合成全氟烷基乙基丙烯酸酯".《化学世界》.2003,(第5期),第263-265页. |
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